DD264210A5 - PROCESS FOR PREPARING 1,5-DIPHENYLPYRAZOLE DERIVATIVES AND A TREATMENT PROCESS FOR PROTECTING CULTURAL PLANTS - Google Patents

Abstract

The invention relates to a process for the preparation of 1,5-Diphenylpyrazolderivaten and a treatment method for protecting crops and herbicidal compositions and their use. An acetophenone of the formula III is reacted in an inert organic solvent in the presence of a base with an equimolar amount of an oxalic acid diester of the formula IV, the resulting Benzoylbenztraubensaeureester with the equimolar amount of phenylhydrazine of formula VI, whereupon the mixture in an acidic medium at elevated temperature for Cyclized 1,5-diphenylpyrazolecarboxylic acid derivative. The use of the agents to control weeds in crops is described. Formulas III, IV, VI

Description

Process for the preparation of 1,5-diphenylpyrazole derivatives and their preparation

Application, the biotope of the invention

The invention relates to a process for the preparation of 1,5-Diphonylpyrazolderivaton and a treatment method for protecting crop plants against the harmful Wirkunc of horbicidally active Phonoxyalkancarbonsuuroestern and herbicidal compositions and their use, these 1, B-diphenylpyrazole-S-carboxylic acid derivatives or a combination of Contains herbicide and 1,5-diphenylpyrazolecarboxylic acid derivative as antagonist «

Chajraktpristik dos b eka nnten state of the art

When phenoxyalkanecarboxylic acid herbicides such as phenoxyphenoxy- and pyridyloxyphenoxy-propionic acid-dianivates are used, crops may show significant differences depending on such factors as dose of herbicide and mode of administration, crop type, soil conditions and climatic conditions such as exposure time, temperature and precipitation Dimensions are damaged. In particular, damage may occur to plants if, in crop rotation, crops which are resistant to the herbicides are cultivated with other crops which have no or only insufficient resistance to the herbicides.

- la

Aim of the invention

The aim of the invention is to reduce the damaging effect of phanoxyalkauecarboxylic acid herbicides on crop plants, in weed-free cereal cultivation and in increasing the yield thereof,

p dos _i LMOs _i s _i ens _i the _i Hrfindync}

The invention is based on the task to produce new 1 .. 5-diphenyl-3-carboxylic acids, esters and iS salt, formulate them ready-to-use agents for agriculture and apply in cereal cultivation together with suitable phenoxypropionyl herbicide for the purpose of weed control.

Ea it has now been found that, surprisingly, a protection of crops against damage caused by herbicidally active phenoxy-propionic acid derivatives, by treatment of crops, parts of these plants or determined for the cultivation of crops with a safener from a group of 1, S-Diphsnylpyrazol-ß-carboxylic acid derivatives can be achieved. Dio herbicidal activity against weeds and grass weeds is not abrogated by these derivatives.

1, ß-diphenylpyrazole-S-carboxylic acid derivatives which are suitable for protecting crop plants from harmful effects of herbicidally active phenoxyphenoxy-, pyridin-2-yloxyphenoxy-, Benzoxazyloxyphenoxy-, Benzthiazolyloxyphenoxy- or Chinoxalinyloxyphenoxypropionsäure derivatives correspond to the formula I.

/ ~ \ N = J-COOR ₁

X> ι ^{τ n} K

(R) -4 i η \ /

wherein R and R are each independently halogen, Ci-Cs-alkyl, Ci-C ₅ ~ Ha.logenalkyl, C ₂ -C5 ~ alkenyl, Cg-Cs-alkynyl or cyano, η is zero or a number from 1 to 3 and the group -ORi represents hydroxy, a salt or any ester radical.

In particular, in the radical -ORi

Ri is hydrogen, a plant-physiologically acceptable metal or ammonium cation, a radical Ci-Cip-alkyl or Cs-Cie-cycloalkyl which is unsubstituted or mono- or polysubstituted by C2-Ce-alkenyl, C2-Ce ~ alkynyl, Ca-Ce-cycloalkenyl , Halogen, nitro, cyano, a radical -XRio, -CXRic, -CX-XRio, -CXNR ₃ Ri ₁ , -XCXRi ₀ , -XCXNR ₃ Ri ₁ , -NR ₃ Ri ₁ , -NR ₃ CONR ₃ R, , -CONR ₃ -NR ₃ (CO) Ri ₄ , Si (Ci-Ci, A.lkyl) ₃ , -C (OR ₇ ) (OR ₈ ) OR ₉ ,

is substituted; a heterocycle, Q of C or N

is bound; an unsubstituted or substituted phenyl or N. phthylrest U, a residual EU or an imido radical -N = C (R ₂ ) R ₂ ,

Ra Ci -Cι, alkyl, Ca-Cv-cycloalkyl or the two R ₂ together a 4-6 membered Ci ₁ -Ci ₂ -alkylene radical branched and / or may be interrupted by oxygen or sulfur Ri and Ri, independently depending is hydrogen, Ci-Ce-alkyl or C3-C8 "cycloalkyl, unsubstituted or substituted by C ₂ -C 6 alkenyl, C ₂ -C ₆ alkynyl, Cs-Cv-Cycloalkyi, halogen, C ₁ -C ₆ -alkoxy, Ca -cg alkoxyalkoxy, Ci-Ce-Alkyithio, cyano, one of C3 and C ₁ and Ci-Ce-alkoxy, -COOR _10, -CONH _2, CONHiCi-CM-alkyl), CON (R ₂₎ Rj, -NH ₂ , -NH (C ₁ -C ₂ -alkyl-N (R ₂ ) R _{2 is} a heterocycle Q is a phenyl or Napthylrest U, which is attached directly or via a C ₁ -C ₁ (, -Alky ^ enbrücke to the nitrogen atom is

R3 and Ri ₄ together form a 4-6-g.Viedrige Ci ₄ -C ₁ 2-alkylene or alkenylene chain which branches and / or by oxygen or sulfur N (C ₁ -Ci, alkyl), N (benzyl), -SO? .- or -CO- or -C (OR ₇ ) OR ₈ may be interrupted and by halogen, C ₁ -C ₁ , alkyl, C ₁ -C ₁ alkoxy, -NH ₂ , -NH (Ci -Ci, -alkyl), -N (Ci-Ci, -Alkyl) ₂ can be substituted, R5 and Re independently of each other Ci-Cij-Alkyl, hydroxy or C ₁ -Ci ₁ -Akoxy

R7 and Re independently each C ₁ -Ci ₁ alkyl, P, 7 and Re together C ₂ -Ci, -Alkylen

R 9 and R 1 are each hydrogen, C ₁ -C 6 -alkyl or C ₃ -C -cycloalkyl unsubstituted or substituted by C ₁ -C 6 -alkenyl, C ₂ -C 6 -alkinyl or C ₃ -C 6 -cycloalkenyl, halogen, C ₁ -C ₁ Alkoxy, C ₂ -C 6 alkoxyalkoxy, C ₁ -C 6 alkoxycarbonyl, C ₁ -C 8 haloalkoxycarbonyl, a heterocycle Q or a phenyl or naphthyl radical U.

Rg and Rio furthermore denote the phenyl or naphthyl radical U or a C-linked heterocycle Q,

Q is a saturated or unsaturated 5-12 membered heterocycle containing 1-4 heteroatoms N, O, S resp. an -SO-, -SO ₂ -, N (Ci-Ci ₁ -AlIyI) - or -N (benzyl) group and by halogen, Ci-Ci »alkyl, Ci-Ci, -Alkoxy, Ci Ci, haloalkyl, Ci-Cu-haloalkoxy, cyano, nitro may be substituted, E is a Ci-Ci, -Alkylen-, Ca-C ^ -Alkenylen- or Cj-Cij-alkynylene bridge,

U is a phenyl or Naphthylreet which is unsubstituted or monosubstituted or polysubstituted by halogen, Ci-Ci, alkyl, X Ci-C ^ -alkyl, Ci-Ci, -alkylsulfinyl, Ci-Ci, -alkylsulfonyl, Ci-Cij -Haloalkyl, Ci-Ci, -haloalkoxy, cyano, nitro, -COOH, -COOCι-Ci, -alkyl, -COCι-Ci ₁ alkyl, CONH ₂ , CONH (Ci-C ι, -alkyl), C0N (Ci -C 1, -alkyl) 2, -SO ₂ NH ₂ , SO ₂ NH (C 1 -C 4 -alkyl), SO ₂ N (C 1 -C 4 -alkyl), pyrrolidino, piperidino or by the pyrrolidinocarbonyl, piperidinocarbonyl, morpholinocarbonyl radical, X oxygen or sulfur.

Plant physiologically compatible metal and ammonium cations are understood to mean the cations of salts customary in herbicides, such as alkali metal, alkaline earth metal, iron, copper, manganese or ammonium alkylammonium, hydroxylalkyl or alkoxyalkylammonium cations.

By alkyl radicals are meant radicals having the stated number of carbon atoms. These radicals can be straight-chain or branched. The most common radicals are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and n-octyl. The alkenyl and alkynyl radicals may also be straight chain or branched and comprise from 3 to 6 carbon atoms. The most common radicals are, for example, allyl, methallyl, butene, butadiene, propynyl, methylpropynyl, 1-butynyl, 2-butynyl. Cycloalkyl- or cycloalkenyl radicals preferably have 3-12 carbon atoms, they can also be benzo-linked. Typical representatives are, for example, cyclopropyl, cyclopentyl, cyclohexyl, cyclohoxenyl, indane, tetrahydronaphthalene, decalin. By halogen is meant fluorine, chlorine, bromine, iodine, in particular fluorine and chlorine. Haloalkyl and haloalkenyl radicals may be monosubstituted or polysubstituted by halogen.

The radical Q is a saturated or unsaturated 5 to 12-membered heterocycle form, the two or three further hetero atoms or a sulfinyl resp. sulfonyl

- 5 -

contains, may be interrupted by one or two carbonyl groups, and which may be benzannellated, unsubstituted or substituted.

As heteroatoms come here a two or three further nitrogen atoms, up to two sulfur or oxygen atoms in question, wherein 2 oxygen atoms can not be directly adjacent

Examples of such heterocycles are listed below: pyrroline, pyrrolidine, imidazoline, imidazolidine, pyrazoline, pyrazolidine, isoxazoline, isoxazolidine, oxazoline, cxazolidine, isothiazolidine, thiazolines, thiazolidines, dithiazolidines, oxadiazolidines, pyridine, piperidine, piperazine, tetrahydropyriroidine and pyrazine, Pyriridine, pyridazine, morpholine, thiomorpholip, thiazines, hexahydrotriazines, tetrahydrotriazines, oxadiazines, oxatriazines, uexahydroazepine, hexahydrodiazepines, diazepines, hexahydrooxazepines, azacyclooctane, benzofuran, benzthiophene, indole, indoline, isoindoline, benzimidazoline, benzindazoline, benzoxazoline, benzthiazolines, benzisoxazoline, benztriazole, Quinoline, tetrahydroquinoline, tetrahydroisoquinoline, quinazoline, quinoxaline, phthalazine, benzmorpholine, benzothiomorpholine, tetrahydrobenzazepines and diazepines, tetrahydrobenzoxazepines, 1,5-diazabicyclo [4,3,0] -nonanes, dihydrobenzoxazines, 1,6-diazabicyclo [5,3, 0] decane, 1,4-diazabicyclo [3,3,0] octane, 1,5-diazabicyclo- [4,4,0 ] Decane.

The above-mentioned heterocycles may also have the meaning of substituents. Further examples of substituent-functional hydrogen-functional systems are, for example, pyrrole, imidazole, pyrazole, isoxazole, oxazole, isothiazole, thiazole, triazoles, oxadiazoles, thiadiazoles, tetrazoles, oxatriazoles, thiatriazoles, furan, tetrahydrofuran, dioxoles, dioxolanes, oxathiols, oxathiolanes, thiophene, tetrahydrothiophene , Dithiolanes, dithiazoles, pyridine, pyrans, thiopyrans, pyridazine, pyrimidine, pyrazine, tetrahydropyran, tetrahydrothiopyran, dioxins, dioxanes, dithiines, dithiane, oxazines, thiazines, oxathiines, oxathiane, triazines, oxadiazines, thiadiazines, oxathiazines, dioxazines, azepines, oxepines , Thiepine, diazepines,

Oxazepines, indoles, benzofurans, benzothiophenes, indazoles, benzimidazoles, benzodioxoles, benzdithiolo, benzisoxazolo, benzthiazoles, benzoxazoles, benzoxathiols, benzotriazoles, benzoxadiazoles. Benzofurazane, benzothiadiazoles, quinoline, isoquinolines, chromenes, chromans, isochromes, isochromans, thiochromenes, isothiochromenes, thiochromans, isothiochromans, cinnoline, quinazoline, quinoxaline, phthalazine, benzodioxines, benzdithiines, benzoxazines, benzdioxanes, bsnzoxathiano, benzotriazines, benzazepines, benzdilazepines, benzoxazepines, purines , Pteridines, phenoxazines, phenothiazines.

The hetorocyclischen radicals may be substituted by halogen, C.-C ₄ -AlUyI, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -HaIOalkyl, C ₁ -C ₄ haloalkoxy, cyano or nitro.

The pyrazole of formula I possess Dorivatö dio ability to crop plants against the damaging action of herbicidally active 2- £ * (4-phenoxy, pyridin-2-yl, benzoxazole benzthiazole _f and quinoxaline-2-yl outstanding degree -oxy) ~ phenoxyjpropionsäure esters of the formula II

(II)

where G

HaI ₂

- '' f ^ 'S- N ^ ^V ' ^Nl Hai., - '? / Ζ- I Il | l or

( ^fi l> n

264 21O

- 6a -

₁ , fluorine, chlorine, bromine, iodine or trifluoromethyl, _{2 is} hydrogen, fluorine, chlorine, bromine or trifluoromethyl, Z is nitrogen or methine -CH =, X is an oxygen or sulfur atom, R 1 is halogen, trifluoromethyl, nitro, cyano, C C 1 -C 4 alkyl, or C 1 -C 2 alkoxy and η O, 1, 2 or 3,

In the compounds of the formula II, halogen, fluorine, chlorine, bromine or clod, preferably fluorine, chlorine and bromine.

_. 7 -

/ Ri ι .CN T is -N ^, -N ^, -OKi ι or -0-N = CRi ₅ Ri6

Τ * 12 Rl3

Ri ι »Ri 2 '' are independently hydrogen, Ci-Ce-alkoxy, Ci-Ce-alkyl, phenyl or benzyl, Ri ι and Ri ₂ together with the sio bearing nitrogen atom, a 5- to 6-membered saturated nitrogen heterocycle, by an oxygen or sulfur atom may be interrupted,

Ri ₃ : Ci-Ci, -Alkyl, C ₃ -Ci, -Alkenyl, C ₃ -Cι, -Alkinyl or C ₂ -Ci ₁ -Akoxyalkyl

Rii ,: hydrogen or the equivalent of an alkali metal, alkaline earth metal copper or iron ion; a quaternary Ci-Ci ₁ -Alkylamraonium- or Ci-C ^ -Hydroxyalkylammonium radical; an optionally mono- or polysubstituted by amino, halogen, hydroxyl, cyano, nitro, phenyl, -CC, alkoxy, polyethoxy having 2 to 6 Aethyler.-oxide units, -COOR, -COSR, -CONH ₂ -, -CON ( _Ci-C) alkoxy) -C _r -C. ₍ -alkyl, -CO-N-di-C 1 -C -alkyl, -CONH-C 1 -C -alkyl, N (C 1 -C 4 -alkoxy) -C 1 -C 4 -alkyl or C 1 -C 4 -cycloalkyl alkylamino-substituted C ₁ -C 9 -alkyl radical; a C ₃ -C 9 -alkenyl radical optionally substituted by halogen or C ₁ -C ₃ -alkoxy; a C ₃ -C 9 -alkynyl radical optionally substituted by halogen or C ₁ -C 4 -alkoxy;

C3-Cg cycloalkyl; or optionally by cyano, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, acetyl, -COORi ₇ , -COSRi ₇ , -CONH ₂ , -CON (C 1 -C 4 -alkoxy) C 1 -C 4 -alkyl, -CO-N-di-Ci-Ci, -alkyl or -CONH-Ci ~ Ci, -alkyl substituted phenyl,

and Ri6 independently of one another Ci-Ci, -alkyl or together a 3 to 6-membered alkylene chain and

Ri7 is hydrogen, Ci-C ₆ -AllCyI, Ci-Ce-haloalkyl, C ₂ -C ₆ alkoxyalkyl, Ca-Ce-alkenyl, Cs-Ce-haloalkenyl, C ₃ -C ₆ -alkynyl or C ₃ -C ₆ -haloalkynyl ,

In the compounds of the formula II, halogen, as an independent substituent or part of another substituent, such as haloalkyl, haloalkoxy, haloalkenyl or haloalkynyl, denotes fluorine, chlorine, bromine or iodine, of which fluorine or chlorine are preferred.

Alkyl is, depending on the number of carbon atoms present, liethyl, ethyl, n-propyl, i-propyl and the isomers butyl, pentyl, hexyl, heptyl or octyl. The alkyl groups contained in the radicals alkoxy, alkoxyalkyl, haloalkyl or haloalkoxy have the same meaning. Preferred are each alkyl group with a low number of carbon atoms.

Preferred haloalkyl radicals or haloalkyl radicals in haloalkoxy radicals are: fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, trichloromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, perfluoroethyl, 2-chloroethyl, 2, 2,2-trichloroethyl, 2-bromoethyl and 1,1,2,3,3,3-hexafluoropropyl.

Cycloalkyl represents mono- and bi-cyclic saturated hydrocarbon ring systems such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, bicyclo [4.3.0] -nonyl, bicyclo [5.2.0] nonyl or bicyclo [2.2.2 .Joktyl.

Particularly noteworthy is the protective effect of pyrazole derivatives of the formula I over such herbicides of the formula II, in which T represents the groups -O-Rm, or -0-N = CRi 5R16, wherein R ₁ 1, hydrogen, Ci-Ci , Alkyl, C3-C1, alkynyl or Ci-Cij-alkyl substituted by Ci-C ^ alkoxycarbonyl or di-Ci-Cij-alkylamino and

and Ri6 independently of one another Ci ~ Ci, alkyl or 5 and Ri6 together denote a C ^ -Cy alkylene chain.

Specific singletons for T are methoxy, ethoxy, propyloxy, isopropyloxy, butyloxy, dimethylaminoethoxy, propargyloxy, 1-cyano-1-methylethoxy, methoxycarbonylmethylthio, 1-ethoxycarbonylethoxy; Butyloxycarbonyl, -ON ^C C (CH ₃ ) 2, -O-N = C (CH ₃ ) C ₂ H ₅ or -ON = C (CH ₂ ) ₅ , and for G

A · ^Α -ι · ^Α · ^Λ ·

Cl- «r) -, I Il H, I Il I,

especially the

2- [4- (6-chlorobenzoxazol-2-yloxy) -phenoxyj-propionic acid ethyl ester,

2- [4- (6-chloroquinoxalin-3-yloxy) "phenoxy] -propionic acid ethyl ester, and the

2- [A- (5-chloro-3-fluoropyridin-2-yloxy) -phenoxy] -propionic acid derivatives of Table 1.

- 10 -

Table 1

Cl- · ⁷ ^ »- O-

(II)

Nt. Y -OCH ₃ physical constant 2.1 -OCijHg-n Mp 63-64 ° C 2.2 -O-N = C (CH ₃ ) ₂ n ³⁵ = 1.5275 2.3 -OC ₂ H ₅ η ³⁵ = 1.5488 2.4 -O-CH ₂ -CH ₂ -N (CH ₃ ) ₂ η ³⁵ = 1.5358 2.5 -O-CH ₂ -C = CH η ³⁵ = 1.5334 2.6 -OC-CN CH ₃ CH ₃ η ³⁵ = 1.5492 2.7 -S-CH ₂ -COOCH ₃ η ³⁵ - 1.5330 2.8 -O-CH-COOC ₂ H ₅ CH ₃ η ³⁵ = 1.5607 2.9 -O-CH ₂ -COOC. »Hg-n ΐΐρ ⁵ = 1.5227 2.10 -OC ₃ H ₇ -n η ³⁵ = 1.5223 2.11 -OC ₃ H ₇ -i "D ⁵ " ¹ ' ⁵³¹⁹ 2.12 -0-N = CC ₂ H ₅ CH ₃ η "» 1.5284 2.13 -O-N = C ( '' \ η ³⁵ «1.5340 2.14. -OCH ₃ (2R) η ^ ⁵ = 1.5360 2.15 -OH η ³⁵ = 1.5359 2.16 -S-CH ₂ -COOCH ₃ (2R) Mp. 95-97 ⁰ C 2.17 "d ^{5 = 1} ^ ⁵⁶²³

- 11 -

Table 1 (continued)

very special is dJo connection 2.19

No. Y physical constant 2.18 2.19 2.20 -O-CH-COOC ₂ H ₅ (2R, S) CH ₃ -O-CH ₂ -ChCH (2R) -NH-OCH ₃ nj ⁵ = * 1.5223 mp 55-56 ° C mp 1O3-1O5 ° C

H ₃ ~. ^ HCOOCH ₂ CsCH

or to emphasize its 2R enantiomer.

The optically active carbon atom of the propionic acid group usually has both R and S configurations. Without particular mention herein is meant the racemic mixtures. Preferred herbicides of formula II are 2R-configured.

As crops which can be protected by 1,5-diphenylpyrazole-3-carboxylic acid derivatives of formula I against damaging effects of herbicides of the formula II, especially those which are important in the food or textile sector, for example sugar cane and in particular Millet, corn, rice and other cereals (wheat, rye, barley, oats).

The invention also relates to the novel 1,5-diphenylpyrazole-3-carboxylic acid derivatives of the formula I.

- 12 -

/ T

/ T ^C00Rl

(R) a η

wherein R and R are each independently halogen, Ci-C Ci-Cs-haloalkyl, C ₂ -C ₅ alkenyl, C ₂ -C ₅ alkynyl or cyano, n is zero or a number from 1 to 3 and Ri the above given With the proviso that when (R) is hydrogen, η is ^a 1 and R 1 is hydrogen or ethyl, R 1, if it is methyl or halogen, must be in the ortho position.

Among these are those of importance in which R, R, and η have the meaning given under the formula I, while Ri Ci-Cia-alkyl or C3-Cio-cycloalkyl unsubstituted or mono- or polysubstituted by C2-co-alkenyl, C ₂ -C _B -alkynyl, C ₁ -C -cycloalkenyl, halogen, nitro, cyano, C ₁ -C 6 -alkoxy, C ₁ -C 4 -alkoxycarbonyl, C ₁ -C 4 -alkylcarbonyl, carbamoyl, di-C 1 -C 6 -alkylcarbamoyl), amino , Ci-Ci, -Alkylamino, di (Ci-Ci, -Alkylamino) a 5-6-membered heterocycle Q which is bound via N or C or a phenyl or Napthylrest U or an Imidorest -N ¹⁵ C (R ₂ ) R ₂ wherein R ₂ Q and U have the meaning given under the formula I with the proviso that if

(R) hydrogen, η = 1 and Ri are hydrogen, (R,) if it is attached to b η

Methyl or halogen means in which must be ortho position.

Very good effect, the 1, S-diphenylpyrazole-ß-carbonsäureesfcer of the formula I in which R, R, and τι given under the formula I.

a ο

While R 1 is C ₁ -C 6 -alkyl, they are unsubstituted or monosubstituted or polysubstituted by C ₂ -C 6 -alkyl, C ₁ -C 6 -alkynyl, halogen, nitro, cyano, C ₁ -C 6 -alkoxy or phenyl, including in particular 1, S-diphenylpyrazole-S-carboxylic acid salts of the formula I in which R, R and η are as defined for formula I and Ri is a plant-physiologically acceptable metal or ammonium cation, in particular 1- (2-chlorophenyl) -3-methoxycar -

264 2) 0

- 13 -

bonyl 5-phenylpyrazole, 1- (2,4-dichlorophenyl) -3-methoxycarbonyl-5-phenylpyrazole, and 1- (2-chlorophenyl-3-raethoxycarbonyl-5- (2-fluorophenyl) pyrazole.

The acid halides of the 1, S-diphenylpyrazole-S-carboxylic acids of the formula I are novel and likewise form an object of this invention.

The 1,5-diphenylpyrazole-3-carboxylic acid derivatives of the formula I can be prepared by various synthesis routes known per se. After one in Ber. ^ 5 3143 (1892) method is prepared 3-ethoxycarbonyl-l, 5-diphenyl-pyrazole ago by condensing molecular amounts of bromoacetophenone and ethyl acetoacetate in the presence of Natriuma'thylat to 2-acetyl-3-benzoylpropionsäureäthylester, to which gives the molecular amount of phenyldiazonium chloride. The condensate, (3 "benzoyl-2-phenylhydrazino-oxime-propionic acid ethyl ester) cyclizes to 3-ethylcarbonyl-1,5-diphene-1-pyrazole in the presence of heat The reaction sequence can be schematically represented as follows:

) - COCH ₂ Br + CH ₃ COCH ₂ COOc ₂ H ₅ '· = · JC ₂ H ₅ ONa

- NhN'Cl + S ^ -COCH ₂ CH-COOC ₂ Hs

OCH ₃

NhNCI + S ^

₂ CC

-COCh ₂ CCOOC ₂ H ₅

HN-N

I

According to another in Ber. ^ 7, 1435 (1914) and Can. J. Chem. 41 , 1813 (1963), the 1,5-diphenyl-pyrazole-3-carboxylic acid and its ethyl ester can be prepared by combining molar amounts of 3-benzoylpropionic acid and acetic anhydride ;, the resulting condensation product is Phenyl-furan-2-carbonyl with

- 14 -

the molar amount of a phenyldiazonium chloride added. The resulting 2-phenylhydrazine-5-phenyl-furfuriliden condensate in the heat to 3 - carboxylic acid-l, 5-diphisnyl-pyrazole or an ester geinäss the scheme

· ' ^ -COCH ₂ CH ₂ COOH + (CH ₃ CO) ₂ O> * {. ^ -C = CH

a £

_t s

.... N = C-COOH y ^J - * v s-k Θ @

⁽ V ί ^(R a ⁾ VhL /> ^{n (R} b>

η ^ \ η ίί \ /

(R) -4 Il ^ö

In these formulas, (R), (R,) and η have the meaning given in formula 1, R 1 is preferably ortho chlorine or para methyl.

According to another method analogous to Ber. ^ O 2185 (1887), one can prepare 1, S-diphenylpyrazole-S-carboxylic acids and their esters by reacting in the presence of a base, e.g. Sodium methylate or ethylate, equimolar amounts of acetophenone and dimethyl oxalate condensed to Benzoylbrenztraubensaureroethylester, to the a'nuimolare amount of a Phenylhydrazines and the condensate in an acidic environment ringschliesst, according to the reaction scheme

~ \ N = C- ⁰⁰⁰⁰ Hs ^^ H ₂ NN- /) ·

/ ~ \ / N = C- ⁰⁰⁰⁰ Hs ^^ H ₂ NN- /)

• · -N ^ I A = I

(Rj 'Η "

a η

In these formulas, R, R, and η have the meaning given to R.

- 15 -

The 1,5-diphenylpyrazole-3-carboxylic acid ester is prepared by reacting an acetophenone of the formula III

< ^R _a > n '~

COCH,

wherein R and η have the meaning given under the formula,, in an inert organic solvent in the presence of a base with the equimolar amount of an oxalic acid diester of the formula IV

R ₁ -OC- ^ OR ₁ (IV)

0 0

wherein R _{1 has} the gec-bene under the formula I meaned dsn Benzoylbenztraubensäureester of formula V

ί-C-CH ₂ -C-COR ₁

· - ^ ooo (ν)

wherein R, R ₁ and η have the meaning given under the formula I with the equimolar amount of phenylhydrazine of the formula VI

{/ VmH-NH ₂ (VI)

^<R b> n

wherein R. and η have the meaning given under the formula 1, whereupon the mixture in an acidic medium at elevated temperature for!, S-Diphenylpyrazolcarbonsäurederlvat the

- 15a -

Formula I cyclized.

For the condensation of the acetophonon and the oxalic acid ester, the inert alcohols are the corresponding alcohols such as methanol, ethanol or acetone, higher-boiling ketones such as methyl ethyl ketone or dioxane, but also higher-boiling ethers such as dipropyl ethers, tetrahydrofuran, and also aromatic hydrocarbons such as benzene, toluene and xylene consideration.

264 23

- 16 -

The cyclization of the condensate of Benzoylbenztrausaureester with the hydrazine is preferably carried out in an acidic medium in glacial acetic acid.

The reaction temperatures are between O ⁰ C and 200 ⁰ C, however, preferably between 0 ⁰ C and the boiling point of the reaction mixture is carried out.

For the preparation of the esters of 1, S-diphenylpyrazole-S-carboxylic acids of formula I following Syntesewege in question

-. N = -COW> _y - _K .N = J-COOR ₁

1. · (V <j + R ₁ OH <> - <j ₊ WH

V \ ⁿ / \

I IJ I IJ

el 3

η η

As acid derivative W, the radicals listed under 1.1 to 1.5 are suitable here.

1.1. Halogen or imidazole residue.

1.2. hydroxy

These reactions proceed smoothly, in part even at room temperature, in a solvent and diluent inert to the reactants. When the acid halide is used, the equimolar amount of a base is added as the acid-binding agent.

When W is hydroxy, a dehydrating agent such as cyclohexyldiimide, sulfuric acid or boiling on a water separator is also suitable.

1.?. Ci-C 1, -Alkoxy.

The reaction is carried out as an acid- or base-catalysed transesterification and, at elevated temperature (room temperature to boiling point), finds an excess of R 2 oil which can also serve as solvent and forms a derivative or alkali of an acid or base

964

- 17 -

instead of. As the solvent, a hydrocarbon such as benzene, toluene or xylene, cyclohexane, an ether such as diethyl ether, tetrahydrofuran or dioxane can be used.

1.4. 0-CO-C ₁ -C ₁ -alkyl.

The reaction of acid anhydrides, like that of the halides, proceeds in some cases even at room temperature in an inert solvent or diluent. At most, the equimolar amount of a base is used as the acid-binding agent.

> N (Ci-Ce-alkyl)

1.5. -o-c;

"NH (C 1 -C ₈ -alkyl)

In this reaction, the amidine radical splits off with the addition of a hydrogen atom as urea. This esterification takes place in an inert anhydrous solvent, preferably in a hydrocarbon such as benzene, toluene, xylene or cyclohexane.

/ ~ \ / T ^C00

T ^C00Rl

HX base

a η

X is halogen or a radical - OSO ₂ (Ci-Ci, -alkyl) in question. The reaction takes place in an organic solvent or diluent, in the presence of a base such as, for example, an alkali metal alcoholate, an alkali metal or alkaline earth metal carbonate or bicarbonate. These bases should not be reactive with RX.

In the following example, the preparation of an inventive 1, S-diphenylpyrazole-S-carboxylic acid theater is described. The temperatures are given in centigrade.

HA 2! O

- 18 -

Examples of further 1, 5-diphenylpyrazole ~ 3-carbon8äuroderivate of the formula are listed in Table 2.

Out of the box

example 1

Hu ^{11 was added to} 1 ~ (2-chlorophenyl) -3-metoxy-carbonyl-5-phenylpyrazole

/ λ ^{Οϋ ο} / -λ, * - * n-j-cooch,

• ν> - NHNH _n + hLCOCCCI LC f ^"Ν \ ..> // \\ _ N

-COCCCH ₀ C- / \ - ρ £ ' \\

(A) 19.3 g (0.105 mol) of 2-chlorophenylhydrazine hydrochloride (97 mol) and 8.6 g (0.105 mol) of a solution of 21.2 g (0.103 mol) Benzoylbrenztrau bensäurGmethylester in 100 ml of glacial acetic acid ) Sodium acetate. After the reaction mixture has been refluxed for 2 hours, it is cooled to room temperature and then poured into Eisvvaeser. The resulting precipitating resin is taken up in ethyl acotate and washed neutral with water and 1 M soda solution. The organic phase is separated, dried over sodium sulfate and concentrated on a rotary evaporator. The remaining oil is crystallized from diisopropyl ether. This gives 17.6 g of title product of melting point 67-70,

The Benzoylbenztraubensöuremethy! Ester required as starting product is manufactured as follows.

- 18a -

/ ^ -C-GH + CHGCOH, -> · / ^N) -CCH ₀ CCOCH,

\ -. / CH ^ OH \ - /

(B) A mixture of 75 ml (0.405 niol) 30% sodium methylate solution and 30 ml of methanol is cooled to 0 ° and while stirring slowly with 48 g (0.4 mol) of acetophenone. To this mixture is added dropwise with stirring at 8-10 °, a solution of 47.2 g (0.4 mol) of dimethyl oxalate in 100 ml of methanol. The reaction mixture becomes cloudy, and finally a yellow thick precipitate forms, which hardly stirs any more. Man gives so much methanol until the reaction mixture stirrable again

- 19 -

becomes. After 3 hours stirring at room temperature is filtered off with suction, the precipitate washed with diethyl ether and sucked dry. The filter material is suspended in water and adjusted to pH 4 with glacial acetic acid with stirring and cooling. The Benzoylbrenztraubensäuremethylester precipitates dabeu. It is filtered off, washed with ice-water and dried in a desiccator over Phcspborpentoxid. This gives 42 g of ester which has a melting point of 56-58 °.

Example 2

Preparation of 1- (2-chlorophenyl) -5-phenyl-pyrazole-3-carboxylic acid chloride.

/ - _N Jt = * - COCl

^cl / ~ \

A mixture of 149.4 g of 1- (2-chlorophenyl) -5-phenylpytazole-3-carboxylic acid and 2000 ml of dry ethylene chloride is heated to 70 °. 40 ml of thionyl chloride are added dropwise with stirring during 12 minutes. The reaction mixture is then refluxed for 2 hrs. ¹ , then cooled to room temperature and evaporated in vacuo. The residue is crystallized from cyclohexane-hexane. This gives 126 g of the above acid chloride, which has a melting point of 101 - 102 °.

- 20 -

V (I)

Table 2 <v η / Il \ \ "1 / η Ri phys. dates No. - 2-C1 CH ₃ Mp. 67 - 70 ° 1 - 2-Cl C ₂ H ₅ 2 - 2-Cl C ₃ H ₇ -n 3 - 2-c: l CK (CH ₃ ) ₂ 4 - 2-Cl CH ₂ CH (CH ₃ ) Z 5 - 2-Cl tetrahydrofurfuryl 6 - 2-Cl CH ₂ CH ₂ CH (CH ₃ ) ₂ 7 - 2-Cl CH ₂ CH (C ₂ Hs) ₂ 8th - 2-Cl CH (CH ₃ ) CH ₂ OCH ₃ 9 - 2-Cl CH ₂ CH ₂ OCH (CHj) ₂ 10 - 2-Cl CH ₂ CH = CH ₂ 11 - 2-Cl CH ₂ C (CH ₃ ) = CH ₂ Mp. 66 - 70 ° 12 - 2-Cl CH ₂ CH ₂ Cl 13 - 2-Cl CH ₂ CH (CH ₃ ) CH ₂ CH ₃ 14 - 2-Cl CH ₂ CsCH Mp. 114-115 ° 15 - 2-Cl CH ₂ CH ₂ CsCH 16 - 2-Cl C (CH ₃ ) ₂ CH ₂ CH ₃ 17 - 2-Cl CH (CH ₃ ) COOCH ₃ 18 - 2-Cl C (CH ₃ ) ₂ COOC ₂ H ₅ 19 - 2-Cl CH ₂ CH ₂ CN 20 - 2-Cl Pyran-2-ylmethyl 21 - 2-Cl benzyl Mp. 142 - 144 ° 22 - 2-Cl CH ₂ CCl ₃ 23 - 2-C1 phenoxyethyl Mp. 8Λ - 91 ° 24 - 2-Cl cyclopropylmethyl 25 - 2-Cl cyclopentylmethyl 26 - 2-Cl 2,2-Dlmethyl-l, 3- 27 dioxolan-4-ylmethyl

- 21 -

"^ O. η η 2-thenyl phya , dates 28 2-Cl CH ₂ CH = CHCl Mp. 147 - 149 ° 29 2-Cl CH ₂ C (Cl) = CH ₂ 30 2-Cl CH ₂ CH ₂ Si (CH ₃ ) ₃ 31 2-Cl CH ₂ Si (CHa) ₃ Mp. 88 - 89 ° 32 2-Cl PyraEol-1-yl-ethyl 33 2-Cl Cr ₂ CH (NO ₂ ) CH ₃ 34 2-Cl CH ₂ CH = CHCH ₃ 35 2-Cl cyclohexyl 36 2-Cl (CH ₂ ) ₉ CH ₃ Srap. 144 - 145 ° 37 2-Cl CH ₂ CH ₂ N (C ₂ Hb) ₂ 38 2-Cl CH ₂ CH ₂ OCH ₂ CH ₂ OC ₂ H ₅ 39 2-Cl CH ₂ CH (Br) CH ₂ Br 40 2-Cl CH (CH ₂ Cl) ₂ 41 2-Cl CH ₂ CH ₂ NO ₂ 42   2-Cl CH ₂ C (CH ₃ ) ₂ N (CH ₃ ) ₂ 43 2-Cl CH (CH ₃ ) CH ₂ N (CHj) ₂ 44 2-Cl 2,6-dimethylcyclohexyl 45 2-Cl 2-furfuryl 46 2-Cl Morpholinoächyl 47 2-Cl CHiCN 48 2-Cl cyclohexylmethyl 49 2-Cl Pyrazol-1-yl-prop-2-yl Mp. 103 - 104 ° 50 2-Cl CH ₂ CH ₂ SO ₂ CH ₃ Mp. 91 - 92 ° 51 2-Cl CH ₂ COOCH ₃ 52 2-Cl CH (CH ₃ ) (CH ₂ ) (, CH ₃ Mp. 143 - 145 ° 53 2-Cl CH (CH = CH ₂ ) (CH ₂ ) I ₁ CH ₃ 25 ⁿ D 1.5470 54 2-Cl CH ₃ 55 2.4 Cl ₂ C ₂ H ₅ Mp. 140 - 143 ° 56 2.4 Cl ₂ CH (CH ₃ ) 2 57 2.4 Cl ₂ CH (CH ₃ ) (CH ₂ ) I ₁ CH ₃ 58 2.4 Cl ₂ CH ₂ CH = CH ₂ 59 2.4 Cl ₂ CH ₂ CsCH 60 2.4 Cl ₂

- 22 -

No. (R _a ) (R ₁₃ ) η η Ri phys. Data egg 2.4 Cl ₂ benzyl 62 2.4 Cl ₂ (CHz) ₇ CH ₃ 63 2.3 Cl ₂ CH ₃ 64 2.3 Cl ₂ C ₂ H ₅ 65 2.3 Cl ₂ CH (CH ₃ ) ₂ 66 2.3 Cl ₂ CH (CH ₃ ) (CH ₂ )., CH ₃ 67 2.3 Cl ₂ CH ₂ CH = CH ₂ 68 2.3 CIz CH ₂ CsCH 69 2.3 Cl ₂ Benzyl (CHz) ₇ CH ₃ 70 2-F CH ₃ mp 83-85 ° 71 2 ~ F C ₂ H ₅ 72 2-F CH (CH ₃ ) z 73 2-F CH (CH ₃ ) (CHz) 1 CH ₃ 74 2-F CH ₂ CH = CH ₂ 75 2-F CH ₂ CHsCH 76 2-F benzyl 77 2-F (CHz) ₇ CiI ₃ 78 2-OCH ₃ CH ₃ mp 126-128 ° 79 2-OCH ₃ C ₂ H ₅ 80 2-OCH ₃ CH (CH ₃ ) ₂ 81 2-OCH ₃ CH (CH ₃ ) (CH ₂ ) 1 CH ₃ 82 2-OCH ₃ CH ₂ CH = CH ₂ 83 2-OCH ₃ CH ₂ CsCH 84 2-OCH ₃ benzyl 85 2-OCHj (CH ₂ J ₇ CH ₃ 86 2.5 Cl ₂ CH ₃ 87 2.5 Cl ₂ C ₂ H ₅ 88 2.5 Cl ₂ CH (CH ₃ ) 2 89 2.5 Cl ₂ CH (CH ₃ ) (CH ₂ ) 1 CH ₃ 90 2.5 Cl ₂ CH ₂ CH = CH ₂ 91 2.5 Cl ₂ CH ₂ C = CH 92 2.5 Cl ₂ benzyl 93 2.5 Cl ₂ (CHz) ₇ CH ₃ 94 2-Cl, 4-CH ₃ CH ₃

- 23 -

No.

<v

<v

Phys. Oaten

95 96 97 98 99

100 -

101 -

102 -

103 -

104 -

105 106 '-

107 -

108 IC

110 111

112 -

113 -

114 115

116 -

117 -

118 -

119 -

120 121

122

123 * ·

124 -

125 -

2-C1, 4-CH ₃

2-Cl, 4-CH ₃

2-Cl, 4-CH ₃

2-Cl, 4-CH ₃

2-Cl, 4-CH ₃

2-Cl, 4-CH ₃

2-Cl, 4-CH ₃

2-Br

2-Br

2-Br

2-Br

2-Br

2-Br

2-Br

2-Br

2-CH ₃

2-CH ₃

2-CH ₃

2-CH ₃

2-CH ₃

2-CH ₃

2-CH ₃

2-CH ₃

2.4 Cl ₂ , 5-OCH ₃

2.4 Cl ₂ , 5-OCH ₃

2.4 Cl ₂ , 5-OCH ₃

2.4 Cl ₂ , 5-OCH ₃

2.4 Cl ₂ , 5-OCH ₃

2.4 Cl ₂ . 5-Ochi

2.4 Cl ,, 5-OCH ₃

2.4 Cl ₂ , 5-OCH ₃

126 3-CH ₃ 2-Cl

127 3-Cl 2 Cl

128 3-OCH ₃ 2-Cl

CH (CH ₃ ) _z

CH (CH ₃ ) (CH ₂ ) KCH ₃

CH ₂ CH = CH ₂

CH ₂ CsCH

benzyl

(CHz) ₇ CH ₃

CH ₃

C ₂ H ₅

CH (CHa) ₂

CH (CH ₃ HCH ₂ KCH ₃

CH ₂ CH = CH ₂

CH ₂ C = CH

benzyl

(CH ₂ ) ₇ CH ₃

CH ₃

C ₂ H ₅

CH (CH ₃ ) ₂

CH (CH ₃ ) (CH ₂ ) ₇ CHi

CH ₂ CH = CH ₂

CH ₂ CsCH

benzyl

(CHz) ₇ CH ₃

CH ₃

C ₂ H ₅

CH (CH ₃ ) ₂

CH (CH ₃ ) (CH ₂ ) I ₁ CH ₃

CH ₂ CH = CH ₂

CH ₂ C = CH

benzyl

(CHz) ₇ CH ₃

CH ₃

CH ₃

CH ₃

Mp. 81 - 83 °

Mp. 105 - 106 ^c

Mp 129-125 ° mp 141-143 ° mp 115-117 °

- 24 -

No. <V (R,) η 2-Cl rl phys. data Ct η 129 3-F 2-NO ₂ CH ₃ Mp 114-116 ° 130 - - CH ₃ Mp 84-85 ° 131 - 2-Cl CH ₃ Mp 208-210 ° 132 - 2-Cl C ₂ H ₅ Mp. 85 - 87 ° 133 - 2-Cl (CH ₂ CH = CHCH ₂ ) ₂ CH ₂ CH (CH ₃ ) ο CH ₃ 134 - 2-Cl -CH ₂ (CH ₂ ) 3 CH = CH ₂ £ 1.5818 135 - 2-Cl 2-chlorobenzyl Mp. 96 - 98 ° 136 - 2-Cl - (CHz) ₇ CH ₃ Dp ⁰ 1.5S32 137 - 2-Cl - (CH ₂ ) H-CH ₃ Mp. 66 - 67 ° 138 - 2-Cl 5-chloro-2-methoxy-phenyl-ethyl Mp. 129 - 130 ' 140 - 2-Cl Pyridin-3-yl Mp 110-111 ° 141 - 2-Cl Pyridin-2-yl 142 - 2-Cl Tetrahydrofuryl-3 Mp. 95 - 97 ° 143 - 2-Cl 5-methyl-thiazol-4-yläthyl Srap. 90 - 91 ° 144 - 2-Cl Thiophen-2-yl-ethyl Mp 123-124 ° 145 - 2-Cl ~ (CH ₂ ) ₃ CH ₃ Mp. 66 - 68 ° 146 - 2-Cl -CH ₂ -CONH ₂ Mp 192-194 ° 147 - 2-Cl - (CH ₂ ) ₈ CH = CH (CH ₂ ) ₇ CH ₃ 148 - 2-Cl HN® (C ₂ Hs) ₃ Mp 163-166 ° 149 2-Cl H ₃ N®CH (CH ₃ ) ₂ Mp. 165 - 168 ° 150 2-Cl 2,3,4,6,7,8,9, -10-octahydropyriinido- [2,1-a] azepine-1-ium Mp 204-206 ° 151 - 2-Cl Na® Mp.> 260 ° 152 - 2-F H Mp. 198 - 200 ° 153 - 2-Cl ORi = Cl (acid chloride) Mp 101-102 ° 154 - - ORi " Cl (acid chloride) 155 3-F - ORi> = Cl (acid chloride) 156 2-F 2-CH ₃ ORi β Cl (acid chloride) 157 2-Cl 2.4 (Cl ORi ° Cl (acid chloride) 158 - ORi »Cl (acid chloride) 159 2-Cl ?.) CH ₃ Mp 84-88 °

264 2tO

- 25 -

No. (R) (R.) Ri phys. Data

η τι

160 2-Cl 2-F CH ₃ mp 84-87 °

161 2-F 3-OCH ₃ CH ₃ Snip. 114-115 °

162 - 3-OCH ₃ CH ₃ mp 103-106 °

163 2F, 4Cl 3-OCH ₃ 'CH ₃ m.p. 82-84'

164 2,4-Clζ 3-OCH ₃ CH ₃ mp 109-111 "

165 - 2- ~ l - <, CHz) i7-CH ₃ m.p. 77-79 ^C

on

166 - 2-Cl - (CHzCH = CCHz-) ₃ H nl 1.5580

CH ₃

167 - 2-Cl-CH (CH ₂ ) 7 CH = CH (CH ₂ ) 7 CH ₃ n £ ² 1.5375

The erfindungsgemäässonon 1, S-Diphenylpyrajiol-S-carboxylic acid derivative of the formula I as a safener in a mixture with 2- [4 ~ (phenyl, pyridin-2-yl ~, 4-Benzoxazo.l-, 4 ~ benzthiazole and 4-quinoxaline -2-yl) oxyphenoxyJ-propionic acid herbicides of the formula II used for controlling weeds in crops of useful plants «

The weeds to be controlled can be both monocotyledonous and dicotyledonous weeds.

As crops or parts of Jieaer plants are, for example, the above> Jn consideration. Areas under cultivation are those which are already overgrown with cultivated plants or seeded with the seed of arable crops, as well as the soils cultivated for the cultivation of these crops.

The application rate Antidot ira ratio to the herbicide depends largely on the type of application. In a field treatment which is carried out using either a tanning mixture with a combination of antidote and herbicide or by separate application of antidote and herbicide, the ratio of antidote to herbicide in the gel is from 1: 100 to 10: 1, preferably

- 26 -

1:20 to 1: 1, and especially 1 .'1, before. In contrast, seed harvests require much lower amounts of antidote in relation to the amount of herbicide per hectare cultivated area.

In the field treatment, 0.01 to 10 kg of antidote / ha, preferably 0.05 to 0.5 kg of antidote / ha, are generally applied.

In seed dressing, 0.01 to 10 g of antidofc / kg of seed, preferably 0.05 to 2 g of antidote / kg of seed, are generally applied. If the antidote is applied in liquid form shortly before Ausoaat under Saraenquellung so conveniently antidote solutions are used which contain the active ingredient in a concentration of 1 bia 10,000, preferably 100 to 1000 ppm.

For application, the compounds of the formula I or combinations of compounds of the formula I with the herbicides to be antagonized are expediently used together with the auxiliaries customary in the art of formulation and are therefore used, for example. to emulsion concentrates, spreadable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, also encapsulations in e.g. polymeric substances, processed in a known manner. The application methods such as spraying, atomizing, dusting, scattering, brushing or pouring are chosen in the same way as the type of means to be used according to the desired goals and the given conditions.

The formulations, i. the active ingredient of formula I or a combination of active ingredient of formula I with antagonizing herbicide and, optionally, a solid or liquid additive containing agent, preparations or compositions are prepared in known manner, e.g. by intimately mixing and / or grinding the active ingredients with diluents, e.g. with solvents, solid carriers, and optionally surface-active compounds (surfactants).

- 27 -

Suitable solvents are: Aromatic hydrocarbons, preferably fractions Ce to C12, e.g. Xylene or substituted naphthalenes, phthalic acid esters such as dibutyl or Dioctylphthalat, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters such as ethanol, Aet'iylenglykol, Aethylenglykolmonomethyl- or -äthyläther, ketones such as cyclol euanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally apoxidized vegetable oils such as epoxidized coconut oil or soybean oil; or water.

As solid carriers, e.g. for dusts and dispersible powders, ground natural minerals are generally used, such as calcite, talc, kaolin, montirorillonite or attapulgite. To improve the physical properties, it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. As granular, adsorptive granule carriers are porous types such. Pumice, broken brick, sepiolite or bentonite, as non-sorptive carrier materials e.g. Calcite or sand in question. In addition, a variety of pre-granulated materials of inorganic or organic nature, in particular dolomite or crushed plant residues can be used.

Suitable surface-active compounds, depending on the nature of the compound of formula 1 to be formulated and optionally also the herbicide to be antagonized, are nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants are also surfactant mixtures.

Suitable anionic surfactants may be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.

As soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (Cio ~ C22), such

 the Na or K salts of OeI- or stearic acid, or of natural

- 28 -

union fatty acid mixtures which can be obtained from coconut oil or tallow ζ.B _one called. Further, fatty acid methyl taurine salts are also mentioned.

More often, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

The fatty sulfonates or sulfates are generally present as alkali, alkaline earth or optionally substituted ammonium salts and have an alkyl radical of 8 to 22 carbon atoms, alkyl also including the alkyl moiety of acyl radicals, e.g. the Na or Ca salt of lignin sulfonic acid, of dodecyl sulfuric acid ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This subheading also covers the salts of sulfuric acid esters and sulfenic acids of fatty alcohol / ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2-sulfonic acid groups and a fatty acid radical having 8 to 22 carbon atoms. Alkylarylsulfonates are e.g. the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or a naphthalenesulfonic acid-formaldehyde condensation products.

Furthermore, corresponding phosphates, e.g. Salts of the phosphoric acid ester of a p-nonylphenol (4-l4) -ethylene oxide adduct or phospholipids in question.

As nonionic surfactants are primarily Polyglykolätherderivate of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols in question, which may contain from 3 to 30 Glykoläthsrgruppen and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.

Further suitable nonionic surfactants are the water-soluble polyethylene oxide adducts containing from 20 to 250 ethylene glycol ether groups and polyethylene oxide adducts containing from 10 to 100 propylene glycol ether groups.

- 29 -

kol, Aethylendiaminopolypropylenglykol and Alkylpolypropylengiykol having 1 to 10 carbon atoms in the alkyl chain, The said compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of nonionic surfactants include nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol,

Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as the polyoxyethylene sorbitan trioleate.

The cationic surfactants are, above all, quaternary ammonium salts which contain as N-substituents at least one alkyl radical having 8 to 22 C atoms and contain, as further substituents, lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. Stearyltrimethylauraoniumchlorid or Benzyldi (2-chloroethyl) ethylammoniumbromid.

The surfactants commonly used in formulation technology are i.a. described in the following publications:

Mc Cutcheon's Detergents and Emulsifiers Annual MC Publishing Corp., Ridgewocd New Jersey, 1981

 Stäche, H., "Surfactant Paperback", Carl Hanser Verlag, Munich / Vienna, 1981.

The agrochemical preparations generally contain 0.1 to 99 weight percent, in particular 0.1 to 95 wt .-%, active ingredient of the formula I or drug mixture antidote / herbicide, 1 to 99.9 wt .-%, in particular 5 to 99, 8 wt .-%, of a solid or liquid additive and 0 to 25 wt .-%, in particular 0.1 to 25 wt .-%, of a surfactant.

264 2tO

- 30 -

While merchandise is more likely to be concentrated, the end user typically uses diluted funds.

The compositions may also contain other additives such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active ingredients to achieve special effects.

For the use of compounds of formula I or compositions containing them for protecting crops against harmful effects of herbicides of formula II, various methods and techniques are contemplated, such as the following:

i) seed dressing

a) heating the seeds with a formulated as a wettable powder of the formula I by shaking in a vessel until the uniform distribution on the seed surface (dry dressing). It uses about 1 to 500 g of active ingredient of the formula I (4 g to 2 kg of spray powder) per 100 kg of seed.

b) dressing the seeds with an emulsion concentrate of the active ingredient of the formula I according to the method a) (wet dressing).

c) pickling by dipping the seed in a broth containing 50-3200 ppm of active ingredient of the formula I for 1 to 72 hours and optionally subsequent drying of the seeds (immersion pickling).

The application of the seed or the treatment of the germinated seedling are naturally the preferred methods of administration because the treatment of the active ingredient is completely directed to the target culture. As a rule, 1 to 500 g of antidote, preferably 5 to 250 g of antidote per 100 kg of seed, are used, whereby: nan can deviate upwards or downwards from the stated limit concentrations, depending on the method, which also allows the addition of other active substances or micronutrients (repeat).

- 31 -

ii) Application from tank mix

A liquid work-up of a mixture of antidote and herbicide (mutual ratio between 10: 1 and 1: 100) is used, wherein the application rate of herbicide from 0.1 to 10 kg per hectare. Such tank mixing is done before or after sowing

applied.

iii) application in the seed furrow

The antidote is introduced as an emulsion concentrate, spray powder or granules in the open seeded seed furrow and then applied after covering the seed furrow in the normal manner, the herbicide in pre-emergence.

iv) Controlled drug delivery

The active ingredient of the formula I is applied in solution to mineral granules or polyarranated granules (urea / formaldehyde) and allowed to dry. Optionally, a coating can be applied (Umgungsungsgranulute), which allows dispensed dosed over a certain period of time.

Formulation example for liquid active substances of the formula I. (% = »Weight percent

1. Enmlsions-Concentrates Active substance from Table 2 Ca-dodecylbenzenesulfonate castor oil polyethylene glycol ether (36 moles of AeO) tributylphonol-polyäthylcnglykoläther (30 moles of AeO) cyclohexanone xylene mixture

From such concentrates, emulsions of any desired concentration can be prepared by dilution with waers.

a) b) c) 50 - 4 25% 40% 6 20 5% O A 20 - - 12% - 15% 65% 25 %

a) b) c) J / θ d) 95 5 - 80 % 10% - - 20% - - - - 70% - - 20% 1 / o - - 94%

2. Solutions

Active ingredient from Table 2

Aethylenglykol monoiiiethyl ether Polyäthylenglykoi MG 400

N-methyl-2-pyrrolidone

Epoxidized coconut oil

Gasoline (boiling limit 160-190 °)

The solutions are suitable for use in the form of very small drops.

3. Granules a) b) Active ingredient from Table 2 5% 10% kaolin. 94% fumed silica 1% attapulgite - 90%

D'.r active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated in vacuo.

4. Dusts a) b) Active substance from Table 2 2% 5% Superdisperse Silica 1% 5% Talc 97% Kaolin - 90%

By intimately mixing excipients with the active ingredient is obtained ready for use i.täubemitel.

- 33 -

Formulierun g sbeispiele for solid active ingredients of formula I

(% a weight percent) a) b) 50 s c) 5. Spray powder 25% 5 5 Ϊ 75% Active ingredient in Table 2 CO / D / 0 - Na ligninsulfonate 3 tu 6 y 5% Na lauryl sulfate - (10% Na Diisobutylnaphthalinsulfonat 2 5 Octylphenolpolyäthylenglykoläther - 10 5 (7-8 moles of AeO) 5% 27 3 £ 10% Highly dispersed silicic acid 62% kaolin

The active ingredient is well mixed with the additives, and milled well in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.

6. Emulsions concentrates

Active ingredient from Table 2 10%

Octylphenolpolyäthylenglykoläther

(4-5 moles of AeO) 3%

Ca-dodecylbenzene sulfonate 3%

Ricinus Polyglycol Ether (35 moles of AeO) 4%

Cyclohexanone 30%

Xylene mixture 50%

From this concentrate emulsions of any desired concentration can be prepared by dilution with water.

7. Dusts a) b) Active substance from Table 2 5% 8% Talc 95%

Kaolin - 92%

- 34 -

Ready-to-use dusts are obtained by mixing the active substance with the excipients and grinding on a suitable mill.

8. extruder granules

Active ingredient from Table 2 10%

Na lignosulfonate 2%

Carboxymethyl cellulose I%

Kaolin 87%

The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in a stream of air.

9. Serving Granules

Active substance from Table 2 3%

Polyethylene glycol (MG 200) 3 %

Kaolin 94%

The finely ground active substance is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.

10. suspension concentrates 40% Active ingredient from Table 2 10% ethylene glycol Nonylphenolpolyäthylenglykolather C 9 / O 'o (15 moles of AeO) 10% Na ligninsulfonate 1 OJ 1 / o carboxymethylcellulose 0.2% 37% aqueous formaldehyde solution Silicone oil in the form of a 75% 0.8% aqueous emulsion 32% water

? "4

- 35 -

The finely ground active substance is mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

Formulation Examples for Active Ingredient Mixtures (Liquid (% by weight)

11. Emulsion Concentrates a) b) c) Active substance mixture: Antidote from Table 2

and a herbicide of Table 1 25% 40% 50%

in the ratio 1: 1

Ca-dodecylbenzenesulfonate 5% 8% 6%

Castor oil pölyäthylenglykolather

(36 moles of AeO) 5%

Tributylphenol polyethylene glycol ether

(30 mol AmO)

cyclohexanone

Xylene linear 65%

From such concentrates, emulsions of any desired concentration can be prepared by dilution with water.

12. Emulsion Concentrates a) b) c) Active substance mixture: Antidote from Table 2

and a herbicide of Table 1 in 25% 40% 50% ratio 1: 3

Ca-dodecylbenzenesulfonate 5.% 8% 6%

Castor oil polyethylene glycol ether

(36 moles of AeO) 5%

Tributylphenol polyethylene glycol ether

(30 moles of AeO)

Cyclohexanone,

Xylene mixture 65%

12 % 4 15% 20 25% 20

12% 4% 15% 20% 25% 20%

264 2tO

- 36 -

From such concentrates, emulsions of any desired concentration can be prepared by dilution with water.

13. Emulsion Kopzentrate a) b) c) active ingredient mixture : Antidote from Table 2

and a herbicide of Table 1 in 25% 40% 50%

Ratio 2: 1

Ca-dodecylbenzene sulphone 5% 8% 6%

Ricinuaöl-polyethylene glycol ether

(36 moles of AeO) 5%

Tributylphenol polyä'thylenglykoläther

(30 moles of AeO) - 12% 4%

Cyclohexanone - 15% 20%

Xylene mixture. , 65% 25% 20%

From such concentrates, emulsions of any desired concentration can be prepared by dilution with water.

14. Emulolone Concentrates a) b) c) Active substance mixture : Antidote from Table 2

and 2- [4- (5-chloro-3-fluoropyridin-2-yloxy) -

phenoxy] propionic acid methylester

in the ratio 1: 1 25% 40% 50%

Ca-dodecylbenzenesulfonate 5% 8% 6%

Castor oil polyethylene glycol ether

(36 moles of AeO) 5%

Iributylphenol-polyethylene glycol ether

(30 moles of AeO)

cyclohexanone

Xylene mixture 65%

From such concentrates dilution with Wasaer emulsions of any desired concentration can be made.

12% 4 15% 20 25% 20

- 37 -

15. Emulsion Concentrate a) b) c) Active substance mixture : Antidote from Table 2

and 2- [4- (5-chloro-3-fluoropyridine-2-yioxy) -phenoxy-propionic acid methylfster

in the ratio 1: 3 25% 40% 50%

Ca-dodecylbenzenesulfonate 5% 8% 6%

Castor oil polyethylene glycol ether

(36 moles of AeO) 5%

Tributylphenol polyethylene glycol ether

(30 moles of AeO)

cyclohexanone

Xylene mixture 65%

From such concentrates, emulsions of any desired concentration can be prepared by dilution with water.

16. Solutions a) b) c) d) Active substance mixture: antidote

Table 2 and a herbicide of

Table 1 in the ratio 1: 4 80% 10% 5% 95%

Ethylene glycol monomethyl ether 20%

Polyethylene glycol MG 400 - 70% -

N-methyl-2-pyrrolidone - 20%

Epoxidized coconut oil - - 1% 5%

Gasoline (boiling 160-190 ⁰ C) - - 94% -

The solutions are suitable for use in the form of very small drops.

12% 4 15 % 20 25% 20

- 38 -

17. Solutions a) b) c) d) Active substance mixture: antidote

Table 2 and a herbicide

Table 1 in the ratio 5: 2 80% 10% 5% 95%

Ethylene glycol monomethyl ether 20%

Polyethylene Glycol MG 400 - 70% -

N-methyl-2-pyrrolidone - 20% -

Epoxidized coconut oil - - 1% 5%

Gasoline (boiling limit 160-19O ⁰ C) - - 94%

The solutions are suitable for use in the form of very small drops,

18. Solutions . a). b) c) d) active substance mixture: antidote

Table 2 and a herbicide

Table 1 in the ratio 1: 1 80% 10% 5 1 95%

Ethylene glycol monoraethyl ether 20%

Polyethylene Glycol MG 400 - 70%

N-methyl-2-pyrrolidone - 20%

Epoxidized coconut oil - - 1% 5%

Gasoline (boiling limit 160-190 ⁰ C) - - 94%

The solutions are suitable for use in the form of very small drops.

- 39 -

19. Solutions a) b) c) d) Active substance mixture: antidote

Table 2 and 2- [4- (5-Chloro-3-

fluoropyridin-2-yloxy) -phenoxy] - 80% 10% 5% 95% methyl propionate

in the ratio 1: 1

Ethylene glycol monomethyl ether 20% - - - ·

Polyethylene Glycol MG 400 - 70%

N-methyl-2-pyrrolidone - 20%

Epoxidized coconut oil - - 1% 5%

Gasoline (boiling limit 160-190 ⁰ C) - - 94%

The solutions are suitable for use in the form of very small drops.

20. Solutions a) b) c) d) Active substance mixture: antidote

Table 2 and 2- [4- (5-Chloro-3-

fluoropyridin-2-yloxy) -phenoxy] - 80% 10% 5% 95%

propionic acid methylester

in the ratio 1: 4

Ethylene glycol monometh / 1-ether 20% -

Polyethylene Glycol MG 400 70%

N-methyl-2-pyrrolidone - 20% -

Epoxidized Kokoonussol - - 1% 5%

Gasoline (boiling limit 160-190 ⁰ C) - - 94% -

The solutions are suitable for use in the form of very small drops.

-AO-

21. Granules a) b) Active substance mixture: Antidote from Table 2

and a herbicide of Table 1 in 5% 10% ratio 1: 1

Kaolin 94%

Highly dispersed silica 1%

Attapulgite - 90%

The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated in vacuo.

22. Granules a) b) Active substance mixture: Antidote from Table 2 and 2-l4- (5-chloro-3-fluoropyridin-2-yloxy) -phenoxyj-propionic acid methyl ester 5% 10% in the ratio 1: 1

Kaolin 94 %

Highly dispersed silica 1%

Attapulgite - 90 %

The active ingredient is dissolved in methylene chloride, sprayed onto the carrier and the solvent is then evaporated in vacuo.

13. Dusts a) b)

Active substance mixture: Antidote from Table 2

and a herbicide of Table 2 in 2% 5%

Ratio 1: 1

Highly disperse silica 1% 5%

Talc 97%

Kaolin - 90%

By mixing the excipients with the active ingredient, ready-to-use dusts are obtained.

- 41 -

Formulation Examples for Active Ingredient Mixtures (Solid )

(% = Weight percent). a) b) c) 75% 24. Spray powder Active substance mixture: Antidote from Table 2 25% 50% - and Gin Herbicide Table 1 im 5% Ratio 1: 1 5% 5% 10% Na ligninsulfonate 3% - Na lauryl sulfate - 6% - Na Diisobutylnaphthalineulfonat 10% Octylphenolpolyäthylenglykoläther - 2% (7-8 moles of AeO) 5% 10% Highly disperse silica 62% 27% kaolin

The active ingredient is well mixed with the additives and ground well in a suitable mill. This gives wettable powder, which can be diluted with water to give suspensions of any desired concentration.

25. Spritzpul ver a) b) c)

Active substance mixture: Antidote from Table 2

and a herbicide of Table 1 in 25% 50% 75%

Ratio 1: 4

Na lignosulfonate 5% 5% -

Na lauryl sulfate Na diisobutyl naphthalene sulfonate Octylphenol polyethylene glycol ether (7-8 mol AeO) Highly dispersed silica Kaolin

3 % - 5 - 6 / o 10 - - 5% 10% 10 62% 27% _{n l}

- 42 -

3% - 5 - 6 « 10 - ώ / 0 - 10% 10 62% 27%

The active ingredient is well mixed with the additives and ground well in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.

26. Spray Powder a) b) c) Active substance mixture: Antidote from Table 2 and a herbicide from Table 1 in 25% 50% 75% ratio 3: 1

Na lignosulphonate 5% 5%

Na lauryl sulfate

Na Diisobutylnaphthalinsulfonat

Octylphenolpolyethylene glycol ether (7-8 moles of AeO)

Highly dispersed silicic acid

kaolin

The active ingredient is well mixed with the additives and ground well in a suitable mill. This gives wettable powders which are diluted with water to give suspensions of the desired concentration.

27. Emulsions Concentrates Active substance mixture: Antidote from Tabrlle 2 and

a herbicide of Table 1 in the ratio 1: 1 10%

Octylphenolpolyethylene glycol ether (4-5 moles of AeO) 3 %

Ca-dodecylbenzenesulfonate 3%

Ricinus Polyglycol Ether (35 moles of AeO) 4%

Cyclohexanone 30%

Xylene mixture 50%

From this concentrate emulsions of any desired concentration can be prepared by dilution with water.

- 43 -

23. Efflulaiona concentrates

Active substance? Antidote from Table 2 and a

Herbicide of Table 1 in the ratio 5: 2 10%

Octylphenolpolyethylene glycol ether (4-5 moles of AeO) 3%

Ca-dodecylbenzenesulfonate 3%

Ricinus Polyglycol Ether (35 moles of AeO) 4%

Cyclohexanone 30%

Xylene mixture 50%

From this concentrate emulsions of any desired concentration can be prepared by dilution with water,

29. Emulsion Concentration Rate

Active substance mixture: Antidote from Table 2 and a

Herbicide of Table 1 in the ratio 1: 4 10%

Octylphenolpolyethylene glycol ether (4-5 moles of AeO) 3%

Ca-dodecylbenzenesulfonate 3 %

Ricinuoölpolyglykoläther (35 mol AeO) 4%

Cyclohexanone 30%

Xylene mixture 50%

From this concentrate emulsions of any desired concentration can be prepared by dilution with water.

30. Dusts a) b) Active substance mixture: Antidote from Table 2 and a

Herbicide of Table 1 in the ratio 1: 1 5% 3%

Talc 95%

Kaolin - 92%

; to Ready for use Stäubetnittol by the active ingredient with the carriers see ver ¹ and is ground in a suitable mill!.

- 44 -

31. Extruder granules

Active substance mixture: Antidote from Table 2 and a

Herbicide of Table 1 in the ratio 1: 1 10%

Na-Ligina sulfonate 2%

Carboxymethylcellulose 1%

Kaolin 87%

The active ingredient is mixed with the additives, ground and moistened with water. This mixture is extruded and then dried in a stream of air.

32. Serving Granules

Active substance mixture: Antidote from Table 2 and a HerbLzid of Table 1 in the ratio 1: 1 3%

Polyethylene glycol (MG 200) 3%

Kaolin · 94%

The finely ground active substance is applied uniformly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.

33. Suspension Concentrates Active substance mixture: Antidote from Table 2 and

In herbicide of Table 1 in the ratio 1: 1 40%

Ethylene glycol 10%

Nonylphenolpolyäthylenglykoläther

(15 moles of AeO) 6%

Na ligrine sulfonate 10%

Carboxymethylcellulose 1%

37% aqueous formaldehyde solution 0.2%

Silicone oil in the form of a 75% aqueous

Emulsion ^ ° ^{σ /}

ι xj ro

Water 32%

2 * 4

The finely ground active substance is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

34. Suspenoion concentrates

Active substance mixture: Antidote from Table 2 and

a herbicide of Table 1 in the ratio 1: 4 40%

Ethylene glycol 10%

Nonyl ^ henolpolyäthylenglykoläther

(15 muI AeO) 6%

Na lignosulphonate 10%

Carboxymethylcellulose 1%

37% aqueous formaldehyde solution 0.2%

Silicone oil in the form of a 75%

aqueous emulsion 0.8%

Water 32%

The finely ground Wirkatoff is intimately mixed with the Zusatzutoffen. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

35. suspension concentrates

Active substance mixture: Antidote from Table 2 and

a herbicide of Table 1 in the ratio 3: 1

ethylene glycol

Nonylphennlpolyäthylenglykoläther

(15 moles of AeO)

Na ligninsulfonate

carboxymethylcellulose

37% aqueous formaldehyde solution

Silicone oil in the form of a 75%

aqueous emulsion

water

40 % 10 % 6 % 10 % 1 % 0 2% O, 8 % 32 %

- 46 -

The finely ground active substance is intimately mixed with the additives. A suspension concentrate is thus obtained from which suspensions of any desired concentration can be prepared by dilution with water.

Biological example l

test Description

In the greenhouse, plastic candles containing 0.5 l of soil are fed with S & mei of the plants to be tested. When the plants have reached the 2 to 3 leaf stage, a safener of formula I and a herbicide of formula II are applied together as a tank mix. 21 days after application, the condition of the plants is scored and the protective effect of the safener is calculated. F.s is the difference in damage caused by the herbicide to a pest that has not been treated with the safener and one that has been treated with safener. The protective effect is stated in percent.

- 47 -

Results culture; Summer wheat "Besso" herbicide:

2 (R) -2- [4- (5-chloro-3-fluoropyridin-2-yloxy) phenoxyJ propionic acid-

propargyl ester (Table 1, 2.19 2R enantiomer)

herbicide g / hg antidote (Table 2) g / ha protection application rate No application rate g / ha 400 001 400 g / ha 75% 2G0 g / ha 75% g / hg IOC g / ha 75% 50 g / ha 75% 200 001 400 g / ha 63% 200 g / ha 75% g / hg 100 g / ha 63% 50 g / ha 75% 100 001 400 g / ha 50% 200 g / ha 63% g / hg 100 g / ha 63% 50 g / ha 63% 400 012 400 g / ha 88% 200 g / ha 75% g / hg 100 g / ha 75% 50 g / ha 75% 200 012 400 g / ha 75% 200 g / ha 75% g / hg 100 g / ha 63% 50 g / ha 63% 100 012 400 g / ha 50% 200 g / ha 63% g / hg 100 g / ha 63% 50 g / ha 63 % 400 024 400 ' g / ha 88% 200 g / ha 88 % 100 88% 50 75%

herbicide antidote (Table 2) .g / ha protection application rate No Aut'wandmenge g / ha 200 g / hg 024 400 g / ha 75% 200 g / ha 7 ^r . % 100 g / ha 75% 50 g / ha 75% 100 g / hg 024 400 g / ha 63% 200 g / ha 63% 100 g / ha 63% 50 g / ha 63% 400 g / hg 036 400 g / ha 50% 200 g / ha 50% 100 g / ha 50% 50 g / ha 38% 200 g / hg 036 400 g / ha 63% 200 g / ha 75% 100 g / ha 75% 50 g / ha 50% 100 g / hg 036 400 g / ha 50% 200 g / ha 50% 100 g / ha 63% 50 g / ha 50% 400 g / hg 049 400 g / ha 63% 200 g / ha 63% 100 g / ha 63% 50 g / ha 38% 200 g / hg 049 400 g / ha 75% 200 g / ha 88% 100 g / ha 75% 50 g / ha 75% 100 g / hg 049 400 g / ha 50% 200 g / ha 63% 100 g / ha 63% 50 g / ha 50 % 400 g / hg 050 400 g / ha 63% 200 g / ha 63% 100 g / ha 50% 50 g / ha 50% 200 g / hg 050 400 g / ha 63% 200 g / ha 75% 100 75%   50 63%

- 49 -

herbicide g / hg antidote (Table 2) protection Aufwandmenga No application rate 100 050 400 g / ha 50% 200 g / ha 50% g / hg 100 g / ha 63% 50 g / ha 38% 400 052 400 g / ha 88% 200 g / ha 75% g / hg 100 g / ha 75% 50 g / ha ' 88% 200 052 400 g / ha 75% 200 g / ha 75% g / hg 100 g / ha 75% 50 g / ha 75% 100 052 400 g / ha 63% 200 g / ha 63% g / hg 100 g / ha 63% 50 g / ha 63% 400 055 400 g / ha 50% 200 g / ha 50% g / hg 100 g / ha 50% 50 g / na 50% 200 055 400 g / ha 63% 200 g / ha 63% g / hg 100 g / ha 75% 50 g / ha 63% 100 055 400 g / ha 63% 200 g / ha 63% g / hg 100 g / ha 63% 50 g / ha 63% 400 070 400 g / ha 63% 200 g / ha 63 % g / hg 100 g / ha 50% 50 g / ha 80% 200 070 400 g / ha 63% 200 g / ha 75% g / hg 100 g / ha 75% 50 g / ha 63% 100 070 400 g / ha 50% 200 g / ha 63% 100 g / ha 50% 50 g / ha 63%

- 50 -

herbicide antidote (Table 2) g / ha protection application rate No Aufwandinenge g / ha 400 g / hg 102 400 g / ha 63% 200 g / ha 75% 100 g / ha 63% 50 g / ha 50% 200 g / hg 102 400 g / ha 63% 200 g / ha 63% 100 g / ha 75% 50 g / ha 75% 100 g / hg 102 400 g / ha 50% 200 g / ha 50% 100 g / ha 50% 50 g / ha 50% 400 g / hg 129 400 g / ha 63% 200 g / ha 63% 100 g / ha 63% 50 g / ha 50% 200 g / hg 129 400 g / ha 63% 200 g / ha 63% 100 g / ha 75% 50 g / ha 50% 100 g / hg 129 400 g / ha 50% 200 g / ha 50% 100 g / ha 50% 50 g / ha 50% 400 g / hg 132 400 , ϊ / ha 75% 200 ₆ / ha 63% 100 g / ha 50% 50 g / ha 38% 200 g / hg 132 400 g / ha 63% 200 g / ha 75% 100 g / ha 63% 50 g / ha 63% 100 g / hg 132 400 g / ha 63% 200 g / hc. 63% 100 g / ha 63% 50 g / ha 63% 400 g / hg 134 400 g / ha 75% 200 g / ba 63% 100 63% 50 38%

- 51 -

herbicide g / hg antidote (Table 2) Schutswirkung application rate No Aufwandmerge 200 134 400 g / ha 75% 200 g / ha 75% g / hg 100 g / ha 75% 50 g / ha 63% 100 134 400 g / ha 50% 200 g / ha 63% g / hg 100 g / ha 50% 50 g / ha 50% 400 135 400 g / ha 88% 200 g / ha 88% K. g / hg 100 g / ha 88% 50 g / ha 88% 200 135 400 g / ha 75% 200 g / ha 75% g / hg 100 g / ha 75% 50 g / ha 75% 100 135 400 g / ha 63% 200 g / ha 63% g / hg 100 g / ha 63% 50 g / ha 63% 400 136 400 g / ha 88% 200 g / ha 88% g / hg 100 g / ha 88% 50 g / ha 88% 200 136 400 g / ha 73% 200 g / ha 75% g / hg 100 g / ha 75 % 50 g / ha 75% 100 136 400 g / ha 63% 200 g / ha 63 % g / hg 100 g / ha 63% 50 g / ha 63% 400 140 400 g / ha 63% 200 g / ha 63% g / hg 100 g / ha 38% 50 g / ha 25% 200 140 400 g / ha 63% 200 g / ha 63% 100 g / ha 63% • 50g / ha 63%

- 52 -

Herbicide Ant amount of exudate No

100 g / hg 140 400 g / hg 143 200 g / hg 143 100 g / hg 143 400 g / hg 144 200 g / hg 144 100 g / hg 144 400 g / hg 149 200 g / hg 149 100 g / hg 149

Ua belle 2) g / ha protection % application rate g / ha sweet 400 g / ha 38 sweet 200 g / ha 50 7a 100 g / ha 50 sweet 50 g / ha 38 % 400 g / ha 63 % 200 g / ha 63 O/ la 100 g / ha 50 V / O 50 g / ha 38 ° / la 400 g / hr. 75 7a 200 g / ha 63 7a 100 g / ha 63 % 50 g / ha 38 S-S 400 g / ha 38 % 200 g / ha 50 % 100 g / ha 50 sweet 50 g / ha 50 7a 400 g / ha 38 sweet 200 g / ha 25 % 100 g / ha 38 % jO g / ha 38 % 400 g / ha 63 % 200 g / ha 63 sweet 100 g / ha 63 % 50 g / ha 63 % 400 g / ha 38 % 200 g / ha 50 % 100 g / ha 50 % 50 g / ha 50 % 400 g / ha 50 sweet 200 g / ha 38 % 100 g / ha 38 % 50 g / ha 25 % 400 g / ha 63 sweet 200 g / ha 63 % 10Ö g / ha 63 % 50 g / ha 38 % 400 g / ha 50 % 200 g / ha 38 % 100 38 50 25

- 53 -

herbicide g / hg antidote (Table 2) g / ha Protective effect application rate No Aufwandnienge g / ha 400 152 400 g / ha 75% 200 g / ha 75% g / hg 100 g / ha 75% 50 g / ha 50% 200 152 400 g / ha 75% 200 g / ha 75% g / hg 100 g / ha 75% 50 g / ha 63% 100 152 400 g / ha 63% 200 g / ha 63% L g / hg 100 g / ha 63% 50 g / ha 50 % 400 160 400 g / ha 63% 200 g / ha 75 % g / hg 100 g / ha 75% 50 g / ha 63% 200 160 400 g / ha 75% 200 g / ha 75% g / hg 100 g / ha 75% 50 g / ha 63% 100 160 400 g / ha 50% 200 g / ha 50 % g / hg 100 g / 'ia 50% 50 g / ha 50% 400 400 g / ha 200 g / ha g / hg 100 g / ha 50 g / ha 200 400 g / ha 200 g / ha g / hg 100 g / ha 50 g / ha 100 400 g / ha 200 g / ha Lotf 50

Claims (12)

claims 1. A process for the preparation of 1,5-Diphenylpyrazolderivaten, characterized in that an acetophenone of the formula III r%. (III) < ^R a> n where I? and η have the meaning given under formula I, in an inert organic solvent in the presence of a base with the equimolar amount of an oxalic acid diester of the formula IV R-OC-C-OR _{1 (1V)} O O wherein R ₁ . has the meaning given under the formula I, the resulting Bonzoylbenztraubensäureester of formula V ., - C-COR, (V) «* ~ · 0 0 0 wherein R, R ₁ and η have the meaning given under the formula I, with the equimolar amount of phenylhydrazine of the formula VI // \\ - NH-NH ₂ (VI) wherein Rj ₃ and η have the meaning given under formula 1, whereupon the mixture in acidic medium at elevated temperature to the 1 _# 5 ~ Diphenylpyra2olcarbonsoeure ~ derivative of the formula I. Nss * -COOR ₁ \ - X \ Vn (I) cyclized wherein R and R. are independently jo halogen, C ₁ -C ₅ -AlkyI ₁ C ₁ -C haloalkyl, C ₃ -C alkenyl, C ₂ -C _c. ~ alkynyl or cyano, η is zero or an integer from 1 to 3 and the group -OR _{1 is} hydroxy or a plant-physiologically acceptable salt or any f -ceter residue, in which R _{1 is} hydrogen, a plant-physiologically valuable metal or ammonium cation, C ₁ -C ₁₃ -AlkYl or C ₃ -C ₁ g-cycloalkyl unsubstituted or mono- or polysubstituted by Cp-Cg-alkenyl, Cg-Cg-alkynyl, C -Cg -cycloalkenyl, halogen, nitro, cyano, a radical -XR ₁₀ I -CXR ₁₀ , -CX-XR ₁₀ , -CXNR ₃ R ₄ , -XCXR ₁₀ , -XCXNR ₃ R ₄ , -NR ₃ R ₄ , -NR ₃ CONR ₃ R ₄ , -CONR ₃ -NR ₃ (CO) ₁₁₁ R ₄ , Si (C ₁ -C ₄ SlKyI) ₃ , -C (OR ₇ ) (OR ₆ ) OR ₉ , PO (R ₅ ) R ₆ , a heterocycle, Q of C or N is an unsubstituted or substituted phenyl or naphthyl radical U, a radical -GU or an imidorost -NaC (R ₂ ) R ₂ , R "C.-C ₄ alkyl, C ₃ -C ₇ cycloalkyl or the two R _{2 to} together form a 4 to 6-membered C.-C 1-4 -alkylene radical which may be branched and / or interrupted by oxygen or sulfur, R ₃ and R ₄ independently of each other hydrogen peroxide, C ₁ -C ₈ alkyl or C_-C ₈ ~ cyclralkyl, unsubstituted or substituted by Cg-Cg alkenyl, C ₂ -C alkynyl, C ^ - alkyl, halogen , C ₁ -C ₄ alkoxy, C ₁ -C ₆ alkoxyalkoxy, alkylthio, cyano, one of C, and also C ₁ -Co -COOR ₁₀ , -CONH ₂ , CONH (C ₁ -C ₄ -alkyl) ₁ CON (R ₂ ) R ₂ , -NH ₂ , -NhI (C ₁ -C ₂ -Okyl-N (R ₂ ) R _{2 is} a heterocyclic Q is a phony 1 or naphthyl radical U, which is directly or via C ₁ -C ₃ - I3t, R, and R ₄ together form a 4- to 6-membered C ₁ -C ₆ -p-alkylene- or alkenylene chain branched and / or represented by oxygen or sulfur M (C ₁ -C ₄ -alkyl), N (benzyl), -S0 ₂ »or -CO- or -C (OR ₇ ) OR ₀ may be interrupted and by halogen, C ₁ -C ₄ -AlkVl, C ₁ -C ₄ -alkoxy, -NL-I ₂ , -NH (C ₁ -C ₄ -allyl), "N (C ₁ -C ₄ -alkyl) ₀ can be substituted, R ₅ and R _fi independently of each other C-C, -alkyl, hydroxy or C. -C ^ alkoxy, R- and Rg independently of one another are each C ₁ -C -alkyl, H ₇ and R ₃ together are C ₁ -C -alkylene, R _q and R ₁₀ each vVasserstof f, C ₁ -C ₃ -alkyl or C _v ~ Cg cycloalkyl, un3iibstituiert or substituted by C ₃ -C alkenyl, C ₂ ~ C _r ~ alkynyl or C -C "cycloalkenyl, Halogen, C ₁ -C ₄ -alkoxy, α, -Cg-alkoxyalkoxy, C ₁ -C ^ -alkoxy carbonyl, C ₁ -C _f -haloalkoxycarbonyl, a hetorocycle Q or a phenyl or naphthyl radical U ₁ Rp and R ₁₀ further denote the phenyl or naphthyl radical U or einon over C-bonded heterocycle Q, Q is a saturated or unsaturated 5- to 12-membered metocycle containing 1 to 4 heteroatoms N ₁ O ₁ S resp. 264 21 ü iso-SO-, -SO ₂ -, N (C ₁ -C ₄ -allyl) or -N (bonzyl) -group, wherein oxygen and sulfur may not be in the vicinal position, and which may be replaced by halogen, C ₁ -C ₄ -AlRyI ₁ C ₁ -C ₄ -alkoxy, C ^ C ^ haloalkyl, C ₁ -C ₄ -HaIoalkoxy, cyano, nitro, e represents a C ₁ -C ₄ alkylene, (^ -C .-alkenylene or p ^c ~ ^C ~ 4 Alkinylenbrücke, U is a phenyl or naphthyl radical which unoubstituiert or mono- or polysubstituted by halogen, C ^ C ^ alkyl, X is C ₁ -C alkyl, sulfinyl _t, C ^^ - alkylsulfonyl, C ₁ -C ₄ -hydroxyl, cyano, nitro, -COOH, -COOC ₁ -C ₄ -alkyl, -COC ₁ -C ₄ -alkyl, ₁ CONH ₂ , CONH (C ₁ -C ₄ -alkyl) ), CON (C ₁ -SO ₂ NH ₂ , SO ₂ MH (C ₁ -C ₄ alkyl), SO ₂ N (C _x -C ₄ alkyl), pyrrolidino, piperidino or by pyrrolidinocarbonyl, piperidinocarbonyl , Norpholinocarbonylrest, X is oxygen or sulfur, with the proviso that when (^ ₆ ) hydrogen, η = 1 and R _{1 is} hydrogen or ethyl, (R) if it means MeIhyl or halogen te in the ortho position must be. 2, Process according to claim 1, characterized in that R, R, and η have the meaning given in formula I, while R _{1 is} hydrogen, a plant-physiologically compatible metal or ammonium cation, C-Cp-alkyl or C -C. -Cycloalkyl, unsubstituiort or mono- or polysubstituted by C ₂ -C ₀ alkenyl, C _? ~ C ₈ -alkynyl, ^G ₃ - ^c ₈ ~ cycloalkenyl, halogen, nitro, cyano, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkoxycarbonyl, C ₁ -C ₄ -alkylcarbonyl, carbonyl, di (C ₁ -C ₄ -) All </ lcarbamoyl), amino, C ₁ -C -alkylamino, di (C ₁ -C -alkylamino), a 5 to 6-membered hoterocycle Q, which is bonded via N or C, or a phenyl or naphthyl radical U, a radical -EU or an imido radical -N = C (R ₂ ) R ₂ , where E, R ", Q and U have the meaning given: iit £ 264 10 It is stipulated that when (^ ₃ ) hydrogen, η = 1 and R 1 are hydrogen or ethyl, (R 1), if it is methyl or halogen, must be in the ortho position. 3. The method according to claim 1, characterized in that one prepares l, 5 ~ diphenylpyrazole-3-carboxylic acid ester of formula I, wherein R ₁ Ri and η have the meaning given, while R _{1 is} C 1 -C ₄ -alkyl, unsubstituted or · or polysubstituted durcp Cp-C ^ alkyl, Cp-C "· - alkynyl, halogen, nitro, cyano C. _t-C alkoxy or phenyl. 4. The method according to claim 1, characterized in that one prepares 1, 5-diphenylpyrazole-3 ~ carboxylic acid salts of the formula I, wherein R ₃ Ru and η have the meaning given and R ^ is a plant-physiologically compatible metal or ammonium cation. -.5-3- Pyridin-2 ~ yl, benzoxazole, benzothiazole and quinoxalin-2 ~ yl-oxy) -phenoxy3propionsäureestern, characterized in that the crop plants, plant parts or the culture surface with a l _# 5-Diph <3nylpyrazol-3-carboxylic acid derivative of Formula I treated and the culture or surface simultaneously or subsequently with a 2- / ^ 4- (phenyloxy, pyridin-2-yloxy, benzoxazolyloxy, Bonzthiazol yyloxy or quinoxalin-2-yloxy phenoxyjpropionsäureestor the formula II CH., G-O- / ^) - O-CH-COT (II) where G or Hal _{1 is} fluorine, chlorine, bromine, ood or trifluoromethyl, Hal _{9 is} hydrogen, fluorine, chlorine, bromine or trifluoromethyl, 2 is nitrogen or methine (-CH =), X is an oxygen or sulfur atom, RL is halogen, trifluoromethyl, nitro »cyano , C.sub.1-C.sub.4-alkyl or C.sub.1-C.-alkoxy and .eta. O, 1, 2 or, and , ^R 11 ^ ^CN T -N ", -N, -OR., Or -0-N = CR ₁₁ R _-1 . V, \ 14 Ib Id ^R 12 ^R 13 where is ^R ll ' ^R 3? are independently hydrogen, C ^ C ^ -C alkoxy _-CG-ß -All <yl, phenyl or benzyl, R ^ and R ^ ₂ together with -60- your nitrogen atom carrying a 5- to 6-membered saturated nitrogen heterocycle, which may be interrupted by an oxygen or sulfur atom, ^R 13 is ^C ₁ - ^C 4 ^{Alky1 'C} ₃ - ^C ₄ - ^{All <s y]} - "C ₃ -C ₄ alkynyl or C ₂ -C ₄ -All <oxy-all <yl, ^R 14 is ^water or the equivalent of an alkali metal, alkaline earth metal, copper or iron ion; a quaternary C ₁ -C. alkylammonium or C ₁ -C 4 -alkylhydroxyalkylammonium radical; an optionally mono- or polysubstituted by amino, halogen, hydroxyl, cyano, nitro, phenyl, C ₁ -C ₄ -alkoxy, polyethoxy having 2 to 6 ethylene oxide units, -COOR, -COSR, -CONH ₂ , -C0N (C ₁ - C ₄ -alkoxy) C ₁ -C ₄ -alkyl _f -CO-Nd! -C ₁ -C ₄ -alkyl, -CuNl-iC ^ C ^ alkyl, -N (C ₁ -C ₄ alkoxy) _T C ₁ -C ₄ alkyl or C ₁ -C ₄ alkylamino-substituted C ₁ -C ₆ -alkyl radical; an optional C «-Cg-alkenyl radical substituted by halogen or C ₁ -C -alkoxy; given a given rolling through halogen or C.-C.-alkoxy substituted C _v -C alkynyl? C -C -cycloalkyl; or optionally by cyano, C ₁ -C ₄ -alkyl, C ₃ -C ₄ -alkoxy, acetyl, -COOR ₁₇ , -COSR ₁₇ , -CONH -C0N (C ₁ -C ₄ -alkoxy) -C ₁ -C ₄ -alkyl, -CO-N-di-Cj-alkyl or -CONH-Cj-C ^ alkyl-substituted phenyl, and R. _ uriabhörifjig each other C ₁ -C ^ -Allyl c (Jer together a 3- to G-linked Alkylonketto and R ₁₇ is hydrogen, C ₁ -C _r alkyl, C ₁ -C haloalkyl, C -C ^ -.- alkoxyalkyl, CC ^ alkenyl, C "" C ₆ haloalkenyl, C ₇ -C ₅ alkynyl, or C 1 -C 4 -alkylhaloalkynyl. 5. The method according to claim I, characterized in that L- (2-chlorophenyl) -3 ~ methoxycarbnnyl "5-phenylpyrazole is prepared, 6. The method according to claim 1, characterized in that l- (2,4-oichlorophenyl) -3 ~ methoxycarbonyl-5-phenylpyrazole is prepared, 7. The method according to claim 1, characterized in that l "is prepared (2-chlorophenyl) - 3-methoxycarbonyl ~ 5 ~ (2-f 1 uorphenyl) pyrazole, 8. Ancestors for the cultivation of cultivated plants against the phytotoxic effect of herbicidally active oil. 9. A method according to claim 8, characterized gekennzoicb.net, that the cultures or their acreage odor simultaneously odor in a short time with a herbicidally effective amount of 2- [ 4 ~ phenyioxy, pyridin-2-yloxy, ßenzoxazolyloxy, üöiizthiazolyloxy or Cliinoxalin-2 -yl-oxy) phanoxyj propion 264 2) 0 acid esters of the formula II and ale antidote with a noror effective Me term of 1, 5-Diphenylpy "" azoi ~ 3-c; arcarboxylic acid derivative of the formula I treated. 10, Selective herbicidal agent for controlling weeds in crops, characterized in that it as a herbicidally active component, a 2- £. 4- (Phenyloxy, pyridin-2-yloxy, Benzoxazolyloxy, Benzthiazolyloxy or quinoxalin-2-yl-oxy) p ! ienoxyj-propionic acid _t ester and containing as an antidote an effective amount of a 1,5-uiph8nylpyrazol-3 ~ carboxylic acid derivative of the formula I together with inert support materials and auxiliaries, 11. A composition according to claim 10, characterized in that it as a herbicidally active component 2- £ 4- (7-chloro-6-fluoropyridln-2-yloxy) -phenoxy) -propiongäure-propargyl ester of the formula CH. w - W " ³ or its 2l? -Gnantiomer contains and as antidote a 1,5 ~ Uiphonylpyrazol-3 ~ carboxylic acid derivative of formula I together with inert Trägsrmatorialien and excipients " 12. A method for selective control of weeds in crops, characterized in that treating the crops or their acreage with an agent according to claim 11.