DD253937A5 - HERBICIDE MEDIUM - Google Patents

Abstract

The invention relates to herbicidal compositions which are novel 1-aryl-pyrazoles of the formula (I) in which X is cyano or nitro, R is cyano or a radical -CO-Y-R1, where the definition of Y and R1 and Ar is taken from the description as containing active ingredients. Formula (I)

Description

Field of application of the invention

The invention relates to herbicidal compositions containing novel 1-aryl-pyrazoles active ingredients.

Characteristic of the known state of the art

It is already known that certain 1-aryl-pyrazoles, such as, for example, 4-cyano-5-propionamido-1- (2,4,6-trichlorophenyl) pyrazole, have herbicidal properties (cf., for example, DE-OS 3226513).

The herbicidal activity of these previously known compounds against weeds, however, as well as their compatibility with important crop plants is not always completely satisfactory in all fields of application.

Furthermore, some 1-aryl-pyrazoles such as 4,5-dicyano-1-phenyl-pyrazole, 5-carboxy-4-nitro-1- (3,4-dichlorophenyl) -pyrazole, the 5'-carboxy- 4-nitro-1-phenylpyrazole which discloses 5-carboxy-4-nitro-1-p-tolylpyrazole and 5-carboxy-4-nitro-1- (3-nitrophenyl) -pyrazole as intermediates (see, Rev. Latinoam Quim., 13, 1-102 [1982]; DE-P 1 229095).

However, nothing is known about a herbicidal activity of these known compounds.

Object of the invention

Surprisingly, the 1-aryl-pyrazoles of the formula (I) according to the invention show a considerable better general herbicidal activity against difficult-to-control weeds and, at the same time, a significantly improved crop plant compatibility in comparison to the 1-aryl-pyrazoles known from the prior art, such as Cyano-5-propionamido-1- (2,4,6-trichlorophenyl) -pyrazole, which are chemically and operatively obvious compounds.

Explanation of the essence of the invention

There have been new 1-aryl-pyrazoles of the general formula (I)

Ar

in which

X is cyano or nitro, R is cyano or a residual CO-YR ¹ , where

Y is oxygen, sulfur or a residual N-

R ²

R ^{1 is} hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl or each optionally substituted cycloalkyl, aralkyl or aryl, is a

stands,

or R ¹ for the case that Y is oxygen, sulfur or a radical -N-SO ₂ -R ³ , also for a salt-bound

inorganic or organic cation,

R ^{2 is} hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkenyl, alkynyl or haloalkenyl, for

each optionally substituted cycloalkyl, aralkyl or aryl, or is a radical SO ₂ -R ³ , wherein each R ³ is optionally substituted alkyl, aralkyl or aryl, R ¹⁰ and R ^{12 are} independently hydrogen or alkyl, R is hydrogen, alkyl Is alkenyl or alkynyl, Z is oxygen, sulfur or an N-alkyl radical and m is a number 1, 2, 3, 4, 5 or 6,

or for a rest

stands,

in which .

R ^{4 is} cyano, nitro, halo, alkyl, alkoxy, alkoxycarbonyl, haloalkyl, haloalkoxy or a radical S (O) _n -R ⁹ .

R ⁵ , R ⁶ , R ⁷ and R ^{8 are} independently hydrogen, cyano, nitro, halo, alkyl, alkoxy, alkoxycarbonyl, haloalkyl,

Haloalkoxy or a ReSt-S (O) _n -R ⁹ where R ^{9 is} alkyl, haloalkyl, amino, alkylamino or dialkylamino and η is a number 0.1 or 2,

found.

Furthermore, it has been found that the new 1-aryl-pyrazoles of the general formula (I)

(D

in which

X is cyano or nitro, R is cyano or a radical -CO-YR ¹ , where

Y is oxygen, sulfur or a residual N-

R ²

R ^{1 is} hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl or each optionally substituted cycloalkyl, aralkyl or aryl, a radical

.12

10

-ZR ¹¹

stands.

or R ¹ for the case that Y is oxygen, sulfur or a radical -N-SO ₂ -R ³ , also for a salt-bound

inorganic or organic cation,

R ^{2 is} hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkenyl, alkynyl or haloalkenyl, for

in each case optionally substituted cycloalkyl, aralkyl or aryl or represents a radical SO ₂ -R ³ , where R ^{3 is} in each case optionally substituted alkyl, aralkyl or aryl, R ¹⁰ and R ¹² independently of one another represent hydrogen or alkyl, R ^{11 represents} hydrogen, Alkyl, alkenyl or alkynyl, Z is oxygen, sulfur or an N-alkyl radical, and m is a number 1, 2, 3, 4, 5 or 6, and Ar is a radical

or for a rest

stands,

R ^{4 is} cyano, nitro, halogen, alkyl, alkoxy, alkoxycarbonyl, haloalkyl, haloalkoxy or an ReSt-S (O) _n -R ⁹ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen, cyano, nitro, Halogen, alkyl, alkoxy, alkoxycarbonyl, haloalkyl,

Haloalkoxy or a radical -S (O) _n -R ⁹ , where R ^{9 is} alkyl, haloalkyl, amino, alkylamino or dialkylamino and η is a number O, 1 or 2, obtained according to the preparation process described below: (a) 5-carboxy-1-aryl-pyrazoles of the general formula (Ia),

(La)

Ar

in which

X and Ar have the meanings given above,

when (a- ) 5-halo-i-aryl-pyrazoles of the formula (II)

in which

X and Ar have the meanings given above and Hal is halogen,

with carbon dioxide in the presence of an organo-lithium compound and in the presence of a diluent; Alternatively, 5-carboxy-4-nitro-1-aryl-pyrazoles of the formula (Ia-1) are obtained,

0OH

(Ia-D

Ar

in which

Ar has the meaning given above.

if (a-j8) 5-methyl-4-nitro-1-aryl-pyrazoles of the formula (III)

JO

IJ

CH-

(III)

Ar

in which

Ar has the meaning given above,

with potassium permanganate in the presence of atmospheric oxygen and in the presence of a diluent in a known manner, or even if (a - 7) B-hydroxy-nitro-i-aryl-pyridazine e-ones of the formula (IV),

(IV)

in which

Ar has the meaning given above,

with bases in the presence of a diluent; or (b) 5-carboxy-1-arylpyrazole derivatives of the formula (Ib-1) are obtained,

1-1

(Lb-1)

in which

X, Y and Ar are as defined above and

R ¹ ~ ^{1 is} alkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl or each optionally substituted cycloalkyl, aralkyl or aryl, is a radical

β 12

»10

stands.

and R ¹¹ for the case in which Y is sulfur or a residual NR ^2, is also hydrogen,

R ^{10 and} R ^{12 are} independently hydrogen or alkyl, R "is hydrogen, alkyl, alkenyl or alkynyl, Z is oxygen, sulfur or an N-alkyl radical and m is a number 1,2,3,4; 5 or 6, if (b- a) the 5-carboxy-1-arylpyrazoles of the formula (Ia) obtainable by processes (a- a), (a- β) or (a-γ) are

(La)

Ar, "

in which

X and Ar are as defined above,

with alcohols, amines or thiols of the formula (V)

(V)

in which

R ¹ ~ ¹ and Y have the abovementioned meaning,

if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent and, if appropriate, in the presence of an acid binder; or salts of the formula (I b - 2) are obtained,

ιθ Θ

(Ib-2)

Ar

in which

X and Ar are as defined above, Y ^{1 is} oxygen, sulfur or a ReSt-N-SO ₂ -R ³ and Μ ^{θ is} an inorganic or organic cation.

if (b - / 3) the 5-carboxy-1-aryl-pyrazole derivatives of the formula ## STR1 ## obtainable by processes (a- a), (a- .beta.), (a-.gamma. ) and (b- a) are obtainable

-Y ¹ -H ₍ l _b)

Ar in which

X, Y ¹ and Ar have the abovementioned meaning,

with inorganic or organic bases, if appropriate in the presence of a diluent in the usual manner; Alternatively, one obtains 1-aryl-pyrazoles of the formula (Ib-3),

-y-RI-2

(Ib-3)

in which X and Ar have the abovementioned meaning and R ¹ " ^{2 is} alkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl or each optionally substituted cycloalkyl, aralkyl or aryl or a

»10

-C-Z-R

11

stands,

R ¹⁰ and R ^{12 are} independently hydrogen or alkyl, R "is hydrogen, alkyl, alkenyl or alkynyl, Z is oxygen, sulfur or N-alkyl and m is 1,2,3,4,5 or 6, if (b - γ) the salts of the formula (I b - 2) obtainable by process (b- β) are

(Ib-2)

in which X, Y ¹ , Μ ^θ and Ar have the abovementioned meaning, with alkylating agents of the formula (VI)

R ¹ " ² -E _t (Vl)

in which

R ¹ " ^{2 has} the meaning given above and

E is an electron attracting leaving group,

optionally in the presence of a diluent; or (c) giving 5-cyano-1-aryl-pyrazole of formula (Ic),

(IO

Ar in which

X and Ar have the meaning given above, if one

(c-α) the 5-carboxamide-i-aryl-pyrazoles of the formula (Ib-4) obtainable by process (b-α),

^ C-NH-, (Ib-4)

Ar in which

X and Ar have the abovementioned meaning, dehydrated by means of customary, generally known methods,

or if you are

(c - ß) 5-halo-1-aryl-pyrazoles of the formula (II).

Ar '

in which

X and Ar have the abovementioned meaning and Hal is halogen, with cyanides of the formula (VII)

; (VII)

in which G® is a suitable counterion, optionally in the presence of a diluent and optionally in the presence of a phase transfer catalyst

implements.

Finally, it has been found that the new 1-aryl-pyrazoles of the general formula (I), herbicidal, in particular also selective

possess herbicidal properties.

The 1-aryl-pyrazoles according to the invention are generally defined by the formula (I). Preference is given to compounds of the formula (I) in which

X stands for cyano or nitro,

R is cyano or a residual CO-YR ¹ ,

Y represents oxygen, sulfur, or a radical N-

R ² -

R ^{1 is} hydrogen, in each case straight-chain or branched alkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkenyl, haloalkenyl or alkynyl having in each case up to 12 carbon atoms and in the case of the haloalkyl or haloalkenyl having 1 to 15 identical or different halogen atoms, for Cycloalkyl having 3 to 7 carbon atoms or in each case optionally mono- or polysubstituted, identically or differently, by halogen, cyano, nitro and in each case straight-chain or branched alkyl, alkoxy, alkylthio or haloalkyl having in each case 1 to 4 carbon atoms and in the case of the haloalkyl having 1 to 9 or phenyl substituted by different halogen atoms, benzyl or phenethyl, furthermore a radical

stands.

and R ¹ for the case where Y is oxygen, sulfur or a radical N-SO ₂ -R ³

is also an equivalent of an alkali, alkaline earth, copper, zinc, manganese, tin, iron, cobalt or nickel cation or an optionally mono- or polysubstituted by identical or different substituted ammonium, phosphonium or Sulfonium cation is, wherein as substituents come into question: straight-chain or branched alkyl having 1 to 18 carbon atoms, phenyl or benzyl;

R ^{2 is} hydrogen, in each case straight-chain or branched alkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkenyl, haloalkenyl or alkynyl having in each case up to 12 carbon atoms and in the case of the haloalkyl or haloalkenyl having 1 to 15 identical or different halogen atoms, for cycloalkyl with 3 to 7 carbon atoms or in each case optionally mono- or polysubstituted by identical or different halogen, cyano, nitro and in each case straight-chain or branched alkyl, alkoxy, alkylthio or haloalkyl each having "1 to 4 carbon atoms and in the case of the haloalkyl with 1 to 9 identical or different halogen atoms substituted phenyl, benzyl or phenethyl, also represents a radical SO ₂ -R ³ , wherein

R ^{3 is} in each case straight-chain or branched alkyl or haloalkyl having in each case 1 to 6 carbon atoms and in the case of the haloalkyl having 1 to 9 identical or different halogen atoms or optionally mono- or polysubstituted by identical or different substituents, phenyl, benzyl or phenylethyl, where as substituents in each case: halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio or halogenoalkyl each having 1 to 4 carbon atoms and in the case of the haloalkyl having 1 to 9 identical or different halogen atoms;

R ¹⁰ and R ¹² are each, independently of one another, hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms,

R ^{11 is} hydrogen or in each case straight-chain or branched alkyl, alkenyl or alkynyl having in each case up to 6 carbon atoms,

Z is oxygen, sulfur or an N-C 1 -C ₄ -alkyl radical and

m is a number 1,2,3,4,5 or 6;

Ar for a rest

or for a rest

stands,

R ⁶

R ^{4 is} cyano, nitro, halogen each represent straight-chain or branched alkyl, alkoxy, alkoxycarbonyl having in each case 1 to 4 carbon atoms, in each case straight-chain or branched haloalkyl or haloalkoxy having in each case 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms or a radical S (O ) _n -R ⁹ stands,

R ⁵ , R ⁶ , R ⁷ and R ⁸ independently of one another represent hydrogen, cyano, nitro, halogen, in each case straight-chain or branched

Alkyl, alkoxy or alkoxycarbonyl having in each case 1 to 4 carbon atoms, in each case straight-chain or branched haloalkyl or halogenoalkoxy having in each case 1 to 4 carbon atoms and 1 to 9 identical or different

Halogen atoms or a radical S (O) _n -R ⁹ , where R ^{9 is} amino, in each case straight-chain or branched alkyl, alkylamino, dialkylamino or haloalkyl having in each case 1 to 4 carbon atoms in the individual alkyl moieties and in the case of the haloalkyl with 1 to 9 same or different

Halogen atoms and η stands for a number O, 1 or 2.

Particular preference is given to compounds of the formula (I) in which X is cyano or nitro,

R is cyano or a radical CO-YR ¹ , where Y is oxygen, sulfur or a residual N-

stands,

R ^{1 is} hydrogen, optionally mono- to trisubstituted, identically or differently by fluorine, chlorine, hydroxyl, methoxy, ethoxy, methylthio or ethylthio-substituted methyl, ethyl, η- or i-penty, n-, i-, s- or tert Butyl, n- or i-propyl, optionally mono- to trisubstituted by identical or different fluorine or chlorine-substituted Al IyI, propenyl or butenyl, propargyl, propynyl, butynyl or pentynyl, cyclopropyl, cyclopentyl, cyclohexyl, in each case optionally substituted one to five times, identically or differently by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, ethoxy, methylthio or trifluoromethyl substituted benzyl or phenyl, a radical

10

»12

-7-rII

-C-Z-R

stands,

and R ¹ for the case that Y is oxygen, sulfur or a radical-N-SO ₂ -R ³ , also for one equivalent of a sodium, potassium, magnesium, calcium, barium, copper, zinc , Manganese, tin, iron, cobalt or an optionally mono- to trisubstituted by identical or different methyl, ethyl, η- or i-propyl, n-, i-, sodert-butyl, benzyl or phenyl-substituted ammonium , Phosphonium or sulfonium cation, represents hydrogen, optionally mono- to trisubstituted by identical or different fluorine, chlorine, hydroxyl, methoxy, ethoxy, methylthio or ethylthio-substituted methyl, ethyl, η- or i-propyl, n-, i, s or tert-butyl, n- or i-pentyl, optionally mono- to trisubstituted by identical or different fluorine or chlorine-substituted Al IyI, propenyl or butenyl, propargyl, propynyl, butynyl or pentynyl, cyclopropyl, Cyclopentyl, cyclohexyl, in each case optionally one to five times, identically or differently, by fluorine, chlorine, bromine, Cyano, nitro, methyl, ethyl, methoxy, ethoxy, methylthio or trifluoromethyl substituted benzyl or phenyl and also a radical

-SO ₂ -R ³

stands, where

R ^{3 represents} methyl, ethyl, n- or i-propyl, n-, i-, s-tert-butyl or optionally mono- to quintuple, identically or differently, by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl , Methoxy, methylthio or trifluoromethyl substituted benzyl or phenyl, ''

R ¹⁰ and R ¹² independently of one another each represent hydrogen, methyl, ethyl, n- or i-propyl,

R "is hydrogen, methyl, ethyl, η- or i-propyl, n-, i-, s- or tert-butyl, allyl, propenyl, butenyl, propargyl, propynyl or butynyl,

Z is oxygen, sulfur, N-methyl or N-ethyl and m is 1,2,3 or 4;

Ar for a rest

or a rest

stands.

R ^{4 is} cyano, nitro, fluoro, chloro, bromo, methyl, ethyl, η- or i-propyl, methoxy, ethoxy, trifluoromethyl, trichloromethyl, dichlorofluoromethyl, chloromethyl, dichloromethyl, difluoromethylpentafluoroethyl, tetrafluoroethyl, trifluorochloroethyl, trifluoroethyl, difluorodichloroethyl, trifluorodichloroethyl, Pentachloroethyl, trifluoromethoxy, dichlorofluoromethoxy, difluorochloromethoxy, chloromethoxy, dichloromethoxy, difluoromethoxy, pentafluoroethoxy, tetrafluoroethoxy, trifluorochloroethoxy, trifluoroethoxy, difluorodichloroethoxy, trifluorodichloroethoxy, pentachloroethoxy, or -S- (O) _n -R ^{9 being} and

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen, cyano, nitro, fluoro, chloro, bromo, methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl , methoxy, ethoxy, trifluoromethyl, trichloromethyl, dichlorofluoromethyl, difluorochloromethyl, chloromethyl, dichloromethyl, difluoromethyl, pentafluoroethyl, tetrafluoroethyl, Trifluorchlorethyl, trifluoroethyl, DifIuordichlorethyl, Trifluordichlorethyl, pentachloroethyl, fürTrifluormethoxy, trichloromethoxy, dichlorofluoromethoxy, difluorochloromethoxy, chloromethoxy, dichloromethoxy, difluoromethoxy, pentafluoroethoxy, tetrafluoroethoxy , Trifluorochloroethoxy, trifluoroethoxy, difluorodichloroethoxy, trifluorodichloroethoxy, pentachloroethoxy or a ReSt-S (O) _n -R ⁹ , where

R ^{9 is} amino, methylamino, ethylamino, dimethylamino, diethylamino, fluorodichloromethyl, difluoromethyl, tetrafluoroethyl, trifluorochloroethyl, trifluoromethyl, methyl or ethyl and

η stands for a number O, 1 or 2.

Very particular preference is given to a group of compounds of the formula (I) in which

X stands for cyano or nitro,

R is cyano or a residual CO-YR ¹ , where Y is oxygen, sulfur or a radical -N-,

R ^{1 is} methyl, ethyl, η- or i-propyl, n-, i-, s- or tert-butyl, n- or i-pentyl, allyl, propenyl, n- or i-butenyl, n- or i-pentenyl , Propargyl, propynyl, n- or i-butynyl, n- or i-pentynyl, trifluoroethyl, trichloroethyl, chloroethyl, chloropropenyl, dichloropropenyl, hydroxyethyl, hydroxypropyl, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, butoxymethyl , Butoxyethyl, methylthiomethyl, methylthioethyl, methylthiopropyl, ethylthioethyl, ethylthiopropyl or propylthioethyl, and also in the event that Y is a radical -N-SO ₂ -R ³ , R ¹

also represents a sodium or potassium ion or an optionally mono- to disubstituted, identical or different by methyl, ethyl, η- or i-propyl, η-butyl or benzyl-substituted ammonium ion;

R ^{2 is} hydrogen, methyl, ethyl, η- or i-propyl, n-, i-, s- or tert-butyl, n- or i-pentyl, allyl, propenyl, n- or i-butenyl, n- or i Pentenyl, propargyl, propynyl, n- or i-butynyl, n- or i-pentynyl, trifluoroethyl, trichloroethyl, chloroethyl, chloropropenyl, dichloropropenyl, hydroxyethyl, hydroxypropyl, methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, methylthiomethyl, methylthioethyl , Methylthiopropyl, ethylthioethyl or ethylthiopropyi, or is a residual SO ₂ -R ³ , wherein

R ^{3 is} methyl, ethyl, p is tolyl or phenyl and

Ar for a rest

or for a rest

stands,

in which '

R ^{4 is} fluorine, bromine or chlorine,

R ⁵ , R ⁷ and R ⁸ are each independently hydrogen, fluorine or chlorine and R ^{6 is} bromo, chloro, methyl, i-propyl, trifluoromethyl, fluorodichloromethyl, trifluoromethoxy or a radical -S (O) _n -R ⁹ stands,

R ^{9 is} methyl or trifluoromethyl and η is a number O, 1 or 2

 Very particular preference is given to a different group of compounds of the formula (I) in which

X is cyano or nitro, R is a radical -CO-YR ¹ ,

in which . ·

Y is oxygen and R ^{1 is} a radical

12

»10

stands,

R ¹⁰ and R ¹² are each independently hydrogen, methyl or ethyl, R ^{11 is} hydrogen, methyl, ethyl, η- or i-propyl, n-, i-, s- or tert-butyl, allyl, propenyl, butenyl , Propargyl, propynyl or butynyl,

Z is oxygen, sulfur, an N-methyl or N-ethyl group and m is a ZahM or 2 and Ar is a radical

or for a rest

stands,

R ^{4 is} fluoro, chloro or bromo, R ⁵ , R ⁷ and R ^{8 are} independently hydrogen, fluoro, chloro or bromo and

R ^{6 is} chloro, bromo, methyl, ethyl, i-propyl, trifluoromethyl, fluorodichloromethyl, trifluoromethoxy or a radical -S (O) _n -R ⁹ where

R ^{9 is} methyl or trifluoromethyl and η is aZaIO, 1 or 2.

Very particular preference is furthermore given to compounds of the formula (I) in which X is cyano or nitro, R is a residual CO-YR ¹ ,

Y stands for oxygen or sulfur and

R ^{1 is} hydrogen or one equivalent of a sodium, potassium, calcium, magnesium, barium, copper, zinc, manganese, tin, iron, cobalt or nickel cation or an optionally one-bis quadrivalent, identically or differently by methyl, ethyl, η- or i-propyl, n-, i- or s-butyl, benzyl or phenyl substituted ammonium cation and

Ar for a rest

or for a rest

stands,

R ^{4 is} cyano, nitro, fluorine, chlorine, bromine, methyl, ethyl, η- or i-propyl, n-, i-, s-or-tert-butyl, methoxy, ethoxy, trifluoromethyl, trichloromethyl, dichlorofluoromethyl, difluorochloromethyl, chloromethyl , dichloromethyl, difluoromethyl, pentafluoroethyl, tetrafluoroethyl ^ ^ rifluorchlorethyLTrifluorethyl.Difluordichlorethyl rifluordichlorethyl, pentachloroethyl, trifluoromethoxy, trichloromethoxy, dichlorofluoromethoxy, difluorochloromethoxy, chloromethoxy, dichloromethoxy, difluoromethoxy, pentafluoroethoxy ^ ^ etrafluorethoxy rifluorchlorethoxy.Trifluorethoxy, Difluordichlorethoxy, Trifluordichlorethoxy, Pentachlorethoxy or a radical-S (O) _n -R ⁹ ,

R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen, cyano, nitro, fluoro, chloro, bromo, methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl , for methoxy, ethoxy, trifluoromethyl, trichloromethyl, dichlorofluoromethyl, difluorochloromethyl, chloromethyl, dichloromethyl, difluoromethyltetafluoroethyl.tetrafluoroethyl.trifluorochloroethyltrifluoroethyl, difluorodichloroethyltrifluorodichloroethyl, pentachloroethyltrifluoromethoxy.trichloromethoxy, dichlorofluoromethoxy, difluorochloromethoxy, chloromethoxy, dichloromethoxy, difluoromethoxy, pentafluoroethoxy, Tetrafluoroethoxy, trifluorochloroethoxy, trifluoroethoxy, difluorodichloroethoxytrifluorodichloroethoxy, pentachloroethoxy or a radical -S (O) _n -R ⁹ , -

R ^{9 is} amino, methylamino, ethylamino, dimethylamino, diethylamino, fluorodichloromethyl, difluoromethyl, tetrafluoromethyl, trichloroethyl, trifluoromethyl, methyl or ethyl

η is a number 0,1 or 2.

In particular, except for the compounds mentioned in the preparation examples, the 1-aryl-pyrazoles of the general formula (I) listed in the following table may be mentioned:

Ar Table II

NO NO NO

CN

CN

CN

CN

CN

COOH

-COO (CH ₂ ) ₃ CH ₃

CF

Table 1 (continued)

NO ₂ -COO (CH ₂ ) ₂ -CH (CH ₃ ) ₂ CN -COO-CH ₂ -SCH ₃

Ar

Cl

CF

Cl

NO-

NO-

NO-

-COO-CH ₂ -OCH ₃

COO ^

CN -CO-NH- (CH ₂ ) ₂ CH ₃

CO-N <

(CH ₂ ) ₂ --CH ₃ (CH ₂ ) ₂ --CH ₃

CN -CO-NH-CH ₅ (CH ₃₎ -COOCH ₂ CN -CH = CH ₂

Cl Cl Cl

Cl

CF

CF

Cl Cl

CF

Cl Cl

--CF--

Cl Cl

 egg

NO ₂ -COOCH ₂ -C = CH ₂

Cl

CN-COOCH ₂ -CF ₃

CF

Cl Cl

Cl

NO ₂ -COO-CH ₂ -C =CH CN -COO-CH ₂ -CH ₂ -OH

Cl

'Cl Cl

Cl

Cl

Table 1 (continued)

Ar

NO ₂ -COO-CH ₂ -CH ₂ -OCH ₃

CN -COO-CH ₂ -CH ₂ -OC ₂ H ₅

OCF

NO ₂ -COO-CH ₂ -CH ₂ -SCH ₃

NO ₂ -CO-NH-SO ₂ CH ₃

CN -COO-CH ₂ -COOC ₂ H ₅

CF

NO-

CN

ΝΟΝΟ-

CN

CF

CF

-COO-CH ₂ -CH ₂ -COOC ₂ H ₅

-COO-CH ₂ -CO-NH-CH ₃

SO ₂ CF ₃

Cl

-COO H ₃ N -CH ₂ -CH (CH ₃ J ₂ ^J ~ ^/ ' ^χ

Cl Cl /

COO® 1/2 Hg ² ® - ^ ^

) ₂ -CO-S-CH ₃

CF

-CO-S-

Cl

NO ₂ -CO-S-CH (CH ₃ ) ₂

Cl Cl

Cl

If, for example, 5-bromo-4-nitro-1- (2,6-dichloro-.4-trifluoromethyl-phenyl) -pyra2ol and carbon dioxide are used as starting materials, the course of the reaction of process (aa) according to the invention can be represented by the following equation :

r ^ N

n-butyl-lithium CO ₂

H ₂ O / K®

If, for example, 5-methyl-4-nitro-1- (2-chloro-4-trifluoromethyl-phenyl) -pyrazole is used as the starting compound, potassium permanganate as the oxidizing agent, the course of the reaction of process (a-β) according to the invention can be represented by the following equation :

KMnO ₄ /

atmospheric oxygen

CF,

If, for example, 5-hydroxy-4-nitro-1- (2,4,6-trichlorophenyl) -pyridazin-6-one is used as starting compound and sodium hydroxide as catalyst, the course of the reaction of process (ay) according to the invention can be described by the following equation represent:

Noo

NaOH

If, for example, 5-carboxy-4-cyano-1- (3,5-dichloropyrid-2-yl) -pyrazole and methanol are used as starting materials and thionyl chloride as reaction auxiliaries, the course of the reaction of process s (ba) according to the invention can be described by the following Represent formula scheme:

SOCl.

+ CH ₃ OH '

-H ₂ O

If, for example, 4-cyano-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazol-5-yl-thiocarboxylic acid and sodium hydroxide are used as starting materials, the course of the reaction of process (b- β) according to the invention can be characterized by represent the following formula scheme:

+ NaOH

-H ₂ O

CF,

CF,

If, for example, 4-cyano-1- (2,4-dichlorophenyl) -pyrazole-5-carboxylic acid potassium salt and 2-bromopropionic acid methyl ester are used as starting materials, the course of the reaction of the process (b-y) according to the invention can be represented by the following formula scheme:

κ®

CH,

Br-CH-COOCH ₃

-KBr

CN CH,

I ³

0-0-CH-COOCH-

If, for example, 4-nitro ^: 1- (2,6-diclptor-4-trifluoromethylphenyl) -pyrazole-5-carboxamide is used as starting compound and phosphorus oxychloride as dehydrating agent, the course of the reaction of process (c) according to the invention can be represented by the following formula scheme:

(POCl ₃ )

-H ₂ O

If, for example, 5-chloro-4-nitro-1- (2,4,6-trichlorophenyl) pyrazole and tetrabutylammonium cyanide are used as starting materials, the course of the reaction of process (c- β) according to the invention can be represented by the following equation:

+ [CH ₃ - (CH ₂ ) ₃ -] ₄ N® CN®

- [CH ₃ - (CH ₂ ) ₃ -] ₄ N® Cl®

Cl

Cl

The 5-halo-i-arylpyrazoles required as starting materials for carrying out the processes (a-a) and (c-.beta.) According to the invention are generally defined by the formula (II). In this formula (II), X and Ar preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.

Hal preferably represents chlorine or bromine.

The 5-halo-1-aryl-pyrazoles of the formula (II) are not yet known. However, they are the subject of our own prior, not yet published patent applications DE-P 3 501323 from 17.1.1985 and DE-P 3520329 from 7.6.1985.

They are obtained, for example, when 5-amino-i-aryl-pyrazoles of the formula (VIII)

(VIII)

in which

X and Ar have the abovementioned meaning, with nitrite compounds of the formula (IX),

R13_O-N = O (IX)

in which R ^{13 is} hydrogen, alkyl or an alkali metal cation, in the presence of a hydrohalic acid ₍ such as hydrochloric or hydrobromic acid or in the presence of a haloform such as chloroform or bromoform at temperatures between -20 ⁰ C and + 80 ° C in the usual manner and Diazotised (see, for example, "Organikum" 15th Edition VEB Deutscher Verlag der Wissenschaften, Berlin 1981 p.652ff; J. Chem. Soc. C, 1966, 1249 or Rev. Latinoam, Quim., 13, 1-102 [1982 ]).

The 5-amino-i-aryl-pyrazoles of the formula (VIII) are known in some cases (cf., for example, EP 26034, EP 53678 or EP 34945 and DE-OS 3226496, DE-OS 3408727, DE-OS 3420985 or DE -OS 3402308), in part they are the subject of their own not yet published patent applications (DE-P 3520327 from 7.6.85 of DE-P 3520330 from 7.6.85).

They are obtained, for example, when aryl-hydrazines of the formula (X)

Ar-NH-NH ₂ (X)

in which

Ar has the abovementioned meaning, (α) with acrylonitrile derivatives of the formula (XI a),

' CN

E ¹ OH = C <

in which

X has the meaning given above and

E ^{1 is} halogen, hydroxy, alkoxy or dialkylamino, or {β) with 2-haloacrylonitriles of the formula (XI b),

CN

CH ₂ = C < _(Xlb)

Shark ¹

in which shark ^{1 is} halogen, in particular chlorine or bromine, first in an I.Stufe, optionally in the presence of a diluent such as, for example, glacial acetic acid or ethanol and optionally in the presence of a ReaktionshilfsmittelSjWie example, sodium acetate at temperatures between -20X and +20 ⁰ C " zli the arylhydrazine derivatives of the formula (XII),

CN

Ar-NH-NH-CH = C < _(XM)

X ¹

in which Ar has the meaning given above and

X ^{I is} halogen, cyano or nitro

and cyclized in a second stage, optionally in the presence of a diluent such as ethylene glycol monoethyl ether and optionally in the presence of an acid catalyst _f such as sulfuric acid or phosphoric acid at temperatures between +50 ⁰ C and + 15O ⁰ C.

The aryl hydrazines of formula (X) may also be optionally cyclized directly in a Reaktiohsschritt, without isolation of the intermediate of formula (XII) in the presence of a diluent, for example, ethylene glycol monoethyl ether or ethanol at temperatures between +50 ⁰ C and + 15O ⁰ C. Optionally, the according to the variant (/ 3) available in the 4-position unsubstituted 5-aminopyrazoles of the formula (XIII),

-NH ₂ (XIII)

Ar __

in which

Ar has the meaning given above,

in a subsequent reaction with a nitrating agent, such as nitric acid, optionally in the presence of a

Diluent such as glacial acetic acid and optionally in the presence of a reaction auxiliary ₍ such as acetic anhydride at temperatures between -20 ° C and + 5O ⁰ C nitrated.

It may be advantageous in this case to protect the amino group in the 5-position of the pyrazole ring before the nitration reaction by conventional protective group technology, for example by acylation and the amino protecting group after nitration also in the usual manner, for example by saponification with aqueous or alcoholic base again secede.

The arylhydrazines of the formula (X) are known (see, for example, U.S. Patent No. 4,127,575, U.S. Patent 3,609,158, West German Patent No. 2,558,399, J. Chem. Soc.

1971, 167-174) or can be obtained in a simple analogous manner by known processes (cf., for example, Houben-Weyl "Methoden der Organischen Chemie", Volume X / 2, p.203, Thieme Verlag Stuttgart, 1967) for example, the known anilines or pyridylamines of the formula (XIV),

Ar-NH ₂ (X'V)

in which

Ar has the meaning given above,

with sodium nitrite in the presence of an acid such as sulfuric acid, and then with tin-II chloride also in the presence of an acid such as hydrochloric acid at temperatures between -20 ⁰ C and +80 ⁰ C or if haloaromatics of formula (XV),

Ar-HaI ² · (XV)

in which

Ar has the abovementioned meaning and Hal ² is halogen, in particular fluorine, chlorine or bromine,

optionally reacted with hydrazine hydrate in the presence of a diluent such as pyridine or dioxane at temperatures between 0 ° C and 150 ⁰ C.

The nitrite compounds of the formula (IX), the acrylonitrile derivatives of the formula (XI a), the 2-haloacrylonitriles of the formula (XI b), the anilines and pyridylamines of the formula (XIV) and haloaromatics of the formula (XV) are generally known Compounds of organic chemistry.

The 5-methyl-4-nitro-1-aryl-pyrazoles required as starting materials for carrying out the process (a- / 3) according to the invention are generally defined by the formula (III). In this formula (III), Ar preferably represents those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for this substituent.

The 5-methyl-4-nitro-1-aryl-pyrazoles of the formula (III) are not yet known. However, they are partially the subject of our own previous unpublished patent application DE-P 3509567 from 16.3.85. The 5-methyl-4-nitro-1-aryl-pyrazoles of the formula (III a)

At which

Ar ¹ for a rest

R ⁵ , R ⁶ , R ⁷ and R ^{8 are} independently hydrogen, cyano, nitro, halo, alkyl, alkoxy, alkoxycarbonyl, haloalkyl,

Haloalkoxy or a radical-S (O) _n -R ⁹ , where R ^{9 is} alkyl, haloalkyl, amino, alkylamino or dialkylamino and η is aZahIO, 1 or 2 stands

 are new.

In the formula (IIIa), R ⁶ , R ^e , R ⁷ , R ⁸ , R ⁹ and η in Ar ^{1 are} preferably or particularly preferably those radicals which have already been used in connection with the description of the substances of the formula (I) according to the invention. have been mentioned as preferred or particularly preferred for these substituents.

5-Methyl-4-nitro-1-aryl-pyrazoles of the formulas (III) and (IIIa) are obtained, for example, when acrylic ester derivatives of the formula (XVI)

COOR ¹⁴ E ² -CH = C <

CO-CH

(XVI)

in which E ^{2 is} alkoxy, in particular methoxy or ethoxy, or dialkylamino, in particular dimethylamino, and R ^{14 is} alkyl, in particular methyl or ethyl, with arylhydrazines of the formula (X)

Ar-NH-NH ₂ . (X)

in which Ar has the abovementioned meaning, first in a first stage, optionally in the presence of a diluent such as ethanol or diethyl ether and optionally in the presence of a reaction auxiliary such as hydrochloric acid at temperatures between -2O ⁰ C and + 2O ⁰ C to the Arylhrazin derivatives of the formula (XVII),

COOR ¹⁴

Ar-NH-NH-CH = C <· (XVII)

CO-CH ₃

in which Ar and R ^{14 have} the abovementioned meaning, and these in a second stage optionally in the presence of a diluent, such as, for example, ethanol and optionally in the presence of a catalyst, such as sulfuric acid, at temperatures between +50 ⁰ C and + 150 ° Ccyclisiert.

The 5-methyl-4-nitro-1-aryl-pyrazoles of the formula (III) can also be used directly in a reaction step without isolation of the intermediate of the formula (XVII), if appropriate in the presence of a diluent ₍ such as, for example, ethanol or

Ethylene glycol monoethyl ether at temperatures between + 5O ⁰ C and + 15O ⁰ C are cyclized.

The B-methyl-pyrazole-carboxylic acid esters of the formula (XVIII) obtainable in this way,

COOR ¹⁴

(XVIII)

in which Ar and R ^{14 have} the abovementioned meaning,

be saponified in the usual manner, for example with bases such as sodium hydroxide or with acids such as hydrobromic acid optionally in the presence of a diluent _t such as ethanol or water at temperatures between -20 ⁰ C and + 100 ° C and the S-methyl pyrazomycarboxylic acids of the formula (XVIIIa),

, L- ^ COOH

^{> vCH} (XVIIIa)

Ar

in which Ar has the meaning given above,

are optionally decarboxylated in the presence of a Verdünnungsmittels.wie such as ethanol or water at temperatures between +100 ⁰ C and +200 ⁰ C, wherein the saponification and subsequent decarboxylation in a reaction step as a so-called "one-pot process" without isolation of the intermediates of formula (XVIIIa) Finally, the thus obtainable 5-methyl-1-aryl-pyrazoles of the formula (XIX),

3 (XIX)

Ar

in which

Ar has the meaning given above,

with a nitrating agent, such as nitric acid optionally in the presence of a diluent such as glacial acetic acid or sulfuric acid and optionally in the presence of a catalyst such as acetic anhydride or sulfuric acid at temperatures between -20 ⁰ C and +150 ⁰ C implemented.

The decarboxylation of the B-methyl-pyrazole ^ -carboxylic acids of the formula (XVIIIa) and the subsequent nitration of the 5-methyl-1-aryl-pyrazoles of the formula (XIX) can likewise be carried out in one reaction step as a so-called "one-pot process" without isolation of the intermediates The acrylic ester derivatives of the formula (XVI) are generally known compounds of organic chemistry (cf., for example, Houben-Weyl "Methoden der organischen Chemie", Vol. VIII, p. 623, Thieme Verlag Stuttgart 4th edition 1952 or Tetrahedron Lett. 25, 3743-3746 [1984]).

For carrying out the process (a-7) required as starting materials ö-hydroxy ^ -nitro-i-arylpyridazin-6-ones are generally defined by the formula (IV). In this formula (IV), Ar preferably represents those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.

The 5-hydroxy-4-nitro-1-aryl-pyridazin-6-ones of the formula (IV) are not yet known.

However, they are obtained in analogy to processes which are known in principle (cf., DE-AS 1195324 and DE-AS 1086238), if mucohalogenic acids of the formula (XXa)

O Hal³ Hal³ H-C-C C-COQH^(XXa>

in which

Hal ^{3 is} halogen, in particular chlorine or bromine,

which is in equilibrium with the corresponding lactone-hemiacetal structure of formula (XXb),

Hal ³ V; r ^ Hal ³

T J ( (XXb)

in which

Hai ^{3 has} the meaning given above,

with arylhydrazines of the formula (X)

Ar-NH-NH ₂ (X)

in which

Ar has the meaning given above,

either first in a first stage, if appropriate in the presence of a diluent such as toluene at temperatures between -2O ⁰ C and +20 ⁰ C to the hydrazones of the formula (XXl),

Hal ³ Hal ³

Il · (XXI)

Ar-NH-N = CH-C C-COOH

in which

Ar and Hai ^{3 have} the meaning given above,

and this, in a second stage, optionally in the presence of a diluent, such as glacial acetic acid, at temperatures of between +100 ⁰ C and + 150 ° Ccyclisiert

or directly in a reaction step, without isolation of the intermediate of formula (XXI), optionally in the presence of a diluent such as toluene or glacial acetic acid and optionally in the presence of a catalyst such as p-toluenesulfonic acid at temperatures between +100 ⁰ C and +200 ⁰ C. cyclized and the thus obtained 4,5-dihalo-pyridazin-6-ones of the formula (XXII),

Shark ³

-Hal ³ · '

(XXII)

in which

Hai ³ and Ar have the meaning given above,. '

with sodium nitrite optionally in the presence of a diluent, such as dimethylformamide at temperatures between + 5O ⁰ C and 18O ⁰ C reacted.

The mucohalogenic acids of the formula (XXa) or (XXb) are generally known compounds of organic chemistry.

For carrying out the process (ba) as starting materials, required 5-carboxy-1-aryl-pyrazoles are by the formula (Ia) X and Ar are preferably those radicals which are already in connection with the description of the compounds of the formula (I) have been mentioned as preferred for these substituents.

The 5-carboxy-1-aryl-pyrazoles of the formula (Ia) are compounds according to the invention and can be obtained by means of the processes (a-a), (a- / 3) or (a-γ) according to the invention.

The alcohols, amines or thiols which are furthermore required as starting materials for carrying out the process (b-a) according to the invention are generally defined by the formula (V). In this formula (V), Y preferably represents those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for this substituent.

R ¹ " ¹ is preferably in each case straight-chain or branched alkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkenyl, haloalkenyl or alkynyl having in each case up to 12 carbon atoms and in the case of haloalkyl or haloalkenyl having 1 to 15 identical or different halogen atoms, for Cycloalkyl having 3 to 7 carbon atoms or each optionally mono- or polysubstituted, identically or differently, by halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio or haloalkyl having in each case 1 to 4 carbon atoms and in the case of the haloalkyl having 1 to 9 or phenyl substituted by different halogen atoms, benzyl or phenethyl, and also a radical

R ¹⁰ and R ¹² are each independently hydrogen or straight or branched alkyl of 1 to 4

R ^{11 is} hydrogen or each is straight-chain or branched alkyl, alkenyl or alkynyl having in each case up to 6 carbon atoms,

Z is oxygen, sulfur, an NC ₁ -C ₄ alkyl radical, and m is a number _1, 2, 3, _4, 5 or 6

R ¹ " ¹ is furthermore for the case that Y is sulfur or a radical NR ² , wherein R ^{2 is} preferably

represents those substituents which have already been mentioned as preferred for this radical in connection with the description of the substances of the formula (I) according to the invention, preferably also for hydrogen. The alcohols, amines or thiols of the formula (V) are generally known compounds of organic chemistry. For carrying out the process (b- / 3) required as starting materials 5-carboxy-i-aryl-pyrazole derivatives are generally defined by the formula (I d). In this formula (I d), X and Ar are preferably those radicals which have already been mentioned as preferred for these substituents in connection with the description of the compounds of the formula (I) according to the invention. Y ¹ is preferably oxygen, sulfur or a ReSt -N-SO ₂ -R ³ ,

where R ³ preferably represents those substituents which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for this radical.

The salts required for carrying out the process (b-7) according to the invention as starting materials are generally defined by the formula (I b-2). In this formula (I b-2), X and Ar preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention. Y ¹ preferably represents those radicals which already mentioned in connection with the description of the precursors of the formula (I d) as being preferred for this substituent, and M® preferably represents one equivalent of a sodium, potassium, magnesium, calcium, barium, copper, zinc , Manganese, tin, iron, cobalt or nickel cations or, for an optionally monosubstituted to trisubstituted, methyl, ethyl, ή- or i-propyl, n-, i-, s- or t-butyl, Benzyl or phenyl substituted ammonium, phosphonium or sulfonium cation.

The salts of the formula (I b-2) are compounds according to the invention and can be obtained by means of the process according to the invention

(B-j8). '

The alkylating agents which are furthermore required as starting materials for carrying out the process (by) according to the invention are generally defined by the formula (VI). In this formula (VI) R ¹ " ² preferably represents those radicals which have already been mentioned in connection with the description of the substances or precursors of the formula (I d) according to the invention as being preferred for this substituent, E is preferably halogen, or in each case optionally halogen-substituted alkylsulfonyloxy or alkoxysulfonyloxy or by halogen or C 1 -C 4 -alkyl-substituted arylsulfonyloxy, in particular chlorine, bromine, iodine, methanesulfonyloxy, methoxysulfonyloxy or p-toluenesulfonyloxy.

The alkylating agents of the formula (VI) are generally known compounds of organic chemistry.

For carrying out the process (c-a) required as starting materials 5-carbonamide-1-aryl-pyrazoles are generally defined by the formula (I b-4). In this formula (I b-4), X and Ar preferably represent those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.

The 5-carboxamide-i-aryl-pyrazoles of the formula (I b-4) are compounds according to the invention and can be obtained by means of the process (b-a) according to the invention.

The 5-halo-i-aryl-pyrazoles of the formula (II) required as starting materials for carrying out the process (c-β) according to the invention have already been described in the description of the process (aa) according to the invention.

The cyanides which are furthermore required as starting materials for carrying out the process {c-β) according to the invention are generally defined by the formula (VII). In this formula (VII), G® is preferably a sodium or potassium cation or an optionally mono- to quadrupole, identically or differently substituted by alkyl having 1 to 12 carbon atoms and / or benzyl-substituted ammonium ion.

The cyanides of the formula (VII) are generally known compounds of organic chemistry.

Suitable diluents for carrying out the process (a-a) according to the invention are inert organic solvents.

These include in particular aliphatic or aromatic hydrocarbons, such as, for example, benzene, benzene, toluene, xylene, petroleum ether, hexane, cyclohexane or ethers such as diethyl ether, dioxane, tetrahydrofuran or Ethylengiykoldimethyl- or diethyl ether.

The process (a-a) according to the invention is carried out in the presence of a suitable organolithium compound. As such, all commonly used for such metallation organolithium compounds such as methyllithium, butyllithium or phenyllithium come into question. Preference is given to using n-butyllithium.

The reaction temperatures can be varied within a certain range when carrying out the process (aa) according to the invention. In general, one works at temperatures between -100 ⁰ C and +50 ⁰ C, preferably at temperatures between -80 ⁰ C and +20 ⁰ C.

To carry out process (aa) according to the invention, 1.0 to 1.5 mol, preferably 1.0 to 1.3 mol, of organolithium compound are generally employed per mole of 5-halo-1-aryl-pyrazole of the formula (II) and 1.0 to 10.0 moles, preferably 1.0 to 5.0 moles of gaseous carbon dioxide.

Initially, the 5-halo-1-aryl-pyrazole of the formula (II) is reacted with the organolithium compound with exclusion of air and moisture in a generally customary manner and then gaseous carbon dioxide is introduced into the reaction mixture. The workup and isolation of the reaction products of formula (I a) is carried out according to generally customary procedures.

Suitable diluents for carrying out the process (a- / 3) according to the invention are, in particular, aqueous solvents. Preferably, aqueous sodium or potassium hydroxide solutions are used.

The reaction temperatures can be varied within a substantial range when carrying out the process (a- / 3) according to the invention. In general, one works at temperatures between 2O ⁰ C and 13O ⁰ C, preferably at temperatures between 6O ⁰ C and 120 ⁰ C.

For carrying out the process (α-β) according to the invention, 1.0 to 10.0 mol, preferably 1.0 to 5, are generally employed per mole of 5-methyl-4-nitro-1-aryl-pyrazole of the formula (III) Add 0 mole of potassium permanganate.

The reaction procedure, workup and isolation of the reaction products of the formula (Ia-I) is carried out in the usual manner (see "Organikum" 15th edition, p.433ff., VEB German Publishers of Sciences, Berlin 1981, see also production examples) ,

Suitable diluents for carrying out the process (a-v) according to the invention are, in particular, aqueous or water-miscible solvents. It is preferable to use alcohols, such as methanol or ethanol, diols, such as ethylene glycol or propanediol, or mixtures thereof with water, ethers, such as tetrahydrofuran or dioxane, or mixtures thereof with water or pure water as solvent.

The process (a-y) according to the invention is carried out in the presence of a base. As such are inorganic or organic bases, such as lithium, sodium, potassium, barium or calcium hydroxide or more basic amines or ammonium bases, such as trimethyl or triethylamine or benzyltrimethylammonium in question.

When carrying out the process (a-γ) according to the invention, the reaction temperatures can be varied within a substantial range. In general, one works at temperatures between 0 ⁰ C and 130 ° C, preferably at temperatures between 20 ° C and 110 ° C.

To carry out the process (ay) according to the invention, 1.0 to 10.0 mol, preferably 1.0, are used per mole of 5-hydroxy-4-nitro-1-arylpyridazin-6-one of the formula (IV) to 5.0 moles of base.

The reaction, work-up and isolation of the reaction products of the formula (Ia-1) is carried out analogously to known processes (cf., DE-AS 1 229095) or Chem. Pharm. Bull. 19, 1635-1640 [1971]).

Suitable diluents for carrying out the process (b-a) according to the invention are inert organic solvents.

These include in particular aliphatic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzene, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, ethers such as diethyl ether, dioxane, tetrahydrofuran or Ethylengiykoldimethyl- or diethyl ether, ketones such as Acetone or butanone, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters such as ethyl acetate, or sulfoxides such as dimethyl sulfoxide.

If alcohols, amines or thiols in liquid form are used as reactants of the formula (V), it is also possible to use them simultaneously in a corresponding excess as diluents.

If appropriate, the process (b-a) according to the invention is carried out in the presence of a suitable reaction auxiliary.

In principle, all customary reaction auxiliaries suitable for esterification and amidation are suitable.

Examples include acid halide such as thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, or active ester components such as N-hydroxy-succinimide, anhydride such as 4-nitrophenyl chloroformate or conventional condensing agents such as dicyclohexylcarbodiimide (DCC), triphenylphosphine in a mixture with carbon tetrachloride, Ν, Ν'-carbonyldiimidazole or N-ethoxycarbonyl-2-ethoxy-dihydroquinoline (EEDQ).

If appropriate, the process (b-a) according to the invention can be carried out in the presence of a suitable acid binder.

As such, all customary inorganic or organic bases are suitable. These include, for example

Alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkali metal carbonates such as sodium carbonate, potassium carbonate or sodium bicarbonate, and tertiary amines such as triethylamine, Ν, Ν-dimethylaniline, pyridine, N, N-

Dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).

A corresponding excess of a simultaneously used as a reactant of the formula (V) amine can

optionally serve as an acid binder.

The reaction temperatures can be varied within a substantial range when carrying out the process (ba) according to the invention. In general, the reaction is carried out at temperatures between 2O ⁰ C and + 15O ⁰ C, preferably at temperatures between ⁰ ° C and + 100 ⁰ C.

For carrying out the process (ba) according to the invention, 1.0 to 20.0 mol, preferably 1.0 to 10.0 mol, of alcohol, amine are generally employed per mole of 5-carboxy-1-aryl-pyrazole of the formula (Ia) or thiol of formula (V), 1.0 to 5.0 mol,

preferably 1.0 to 2.0 moles of reaction auxiliary and optionally 1.0 to 2.0 moles of acid binder.

In most cases, it is advantageous first of the 5-carboxy-1-aryl-pyrazoles of the formula (Ia) and the

Reaction aid according to conventional methods to produce an activated complex (acid halide, active ester, mixed acid anhydride, etc.), which can optionally be isolated and either in a separate reaction step or in

One-pot process is reacted with the alcohol, amine or thiol of formula (V). The addition of the acid binder can

depending on the reaction auxiliary used either in the I.Stufe for the formation of the activated complex or in the

2nd stage to implement the same useful. The reaction procedure, work-up and isolation of the reaction products of the formula (Ib-1) is carried out according to generally customary procedures.

Suitable diluents for carrying out the process (b- / 3) according to the invention are organic or aqueous

Solvent or organic-aqueous solvent mixtures in question. It is preferable to use alcohols such as methanol, ethanol or propanol or mixtures thereof with water and pure water as a diluent.

The process (b- / 3) according to the invention is usually carried out in the presence of an inorganic or organic base

carried out. As such, one uses hydroxides, oxides or carbonates of alkali or alkaline earth metals or suitable

substituted amines, depending on the nature of the desired counterion M® in the compounds of formula (Ib-2).

When carrying out the process (b-β) according to the invention, the reaction temperatures can be varied within a substantial range. In general, one works at temperatures between -2O ⁰ C and +120 ⁰ C, preferably at temperatures between ^{0 0} C and 8O ⁰ C.

To carry out the process (b- / 3) according to the invention, use is made of per mole of 5-carboxy-1-aryl-pyrazole derivative

Formula (Id) is generally 1.0 to 20.0 moles, preferably 1.0 to 10.0 moles, of base.

The calcium, barium, magnesium, manganese, copper, nickel, tin, iron and cobalt salts are also obtained from the

Sodium salts by treatment with a corresponding inorganic metal salt, e.g. Calcium chloride, barium chloride,

Copper sulfate, nickel chloride or cobalt nitrate.

The workup and isolation of the salts of formula (I b-2) is carried out by conventional methods.

Suitable diluents for carrying out the process (b-β) according to the invention are inert organic solvents.

These include in particular aliphatic or aromatic, optionally halogenated hydrocarbons such as

for example, benzene, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform,

Carbon tetrachloride, ethers such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether. Ketones such as acetone or butanone, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, dimethylacetamide, N-butyl

Methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters such as ethyl acetate or sulfoxides such as dimethyl sulfoxide.

The reaction temperatures can be varied within a substantial range when carrying out the process (by) according to the invention. In general, one works at temperatures between 0 ⁰ C and + 18O ⁰ C, preferably at temperatures

between + 20 ^° C. and + 150 ^° C.

For carrying out the process (b-γ) according to the invention, 1.0 to 10.0 mol, preferably 1.0 to 5.0 mol, of alkylating agent of the formula (VI) are generally employed per mole of salt of the formula (Ib-2) on. The reaction is carried out, working up and isolation of the reaction products of formula (I b-3) by customary and known methods.

Suitable dehydrating agents for carrying out the process (ca) according to the invention are all customary ones

Amide dehydration useful systems in question.

Examples which may be mentioned are triphenylphosphine / carbon tetrachloride (cf., for example, Chem. Ber., 105, 244-256 [1972], Tetrahedron

Letters 1970, 4383-4384); Thionyl chloride (see B. B. Organic Syntheses Coll.4.436-438 [1963]), p-toluenesulfonyl chloride / pyridine (see, for example, J. American Chem. Soc., 77, 1701-1702 [1955]), phosgene / Pyridine, (J.Chem.Soc. 1954, 3730);

Dicyclohexylcarbodiimide (J. Org. Chemistry 26, 3656-3360 [1961]); Phosphorus pentoxide (Organic Syntheses Coll. Vol. 4,144

[1963]), phosphorus oxychloride / sodium bisulfite (J. Org. Chemistry 22, 1142 [1957]), phosphorus pentachloride (Organic

Syntheses Coll. Vol. II, 379 [1943]), acetic anhydride (J. Amer. Chem. Soc., 71, 2650-2652 [1949]) or oxalyl chloride / pyridine (Synth.

Commun. 10,479-487 [1980]).

The diluents used in this case are generally dependent on the dehydrating agent used.

Usually, inert organic solvents are used.

These include in particular aliphatic or aromatic, optionally halogenated hydrocarbons such as

for example, benzene, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform,

Carbon tetrachloride, ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, ketones, such as acetone or butanone, nitriles, such as acetonitrile or propionitrile, amides, such as dimethylformamide, dimethylacetamide, N-

Methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters such as ethyl acetate or sulfoxides such as dimethyl sulfoxide.

In carrying out the process (c-a) according to the invention, the reaction temperatures may vary depending on

used dehydration system can be varied in larger areas. In general, one works at temperatures between -20 ⁰ C and +200 ⁰ C, preferably at temperatures between 0 ⁰ C and +180 ⁰ C.

For carrying out process (c) according to the invention, in general 1.0 to 30.0 mol, preferably 1, are employed per mole of 5-carboxamide-i-aryl-pyrazole of the formula (I b-4), depending on the dehydration method used. 0 to 15.0 moles of dehydrating agent. The work-up and isolation of the reaction products of the formula (Ic) is carried out in analogy to known processes (see also Harrison, Harrison "Compendium of Organic Synthetic Methods" Vol. 1, pp. 464-465 [1971]; Patai "The Chemistry of the Cyano-Group "pp. 96-103 Interscience 1970; Ferri" Reactions of Organic Synthesis "p.240, Thieme Verlag Stuttgart 1978).

Suitable diluents for carrying out the process (c- / 3) according to the invention are inert organic solvents or organic-aqueous two-phase mixtures.

These include, in particular, aliphatic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzene, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether, ketones, such as Acetone or butanone, nitriles such as acetonitrile or propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters such as ethyl acetate or sulfoxides such as dimethyl sulfoxide or organic-aqueous two-phase mixtures such as toluene-water or dichloromethane-water. The addition of from 0.01 to 10% by weight (based on the 5-halo-i-arylpyrazole of the formula [H] used) of a phase transfer catalyst may prove advantageous in some cases. As examples of such catalysts may be mentioned:

Tetrabutylammonium iodide, etrabutylammonium bromide, ributylmethylphosphonium bromide, trimethyl-Ci ₃ / Ci ₅ -alkylammonium chloride, dibenzyl-dimethylammonium methylsulfate, dimethyl-C 1 -C 6 -alkyl-benzylammonium chloride, tetrabutylammonium hydroxide, 18-crown-6, triethylbenzylammonium chloride, trimethylbenzylammonium chloride. The reaction temperatures can be varied within a substantial range when carrying out the process (c-β) according to the invention. In general, one works at temperatures between 0 ^{c C} and 100 ⁰ C, preferably at temperatures between 10 ⁰ C and 8O ⁰ C.

For carrying out the process (c-β) according to the invention, 1.0 to 10.0 mol, preferably 1.0 to 5.0 mol, are generally employed per mole of 5-halo-i-aryl-pyrazole of the formula (II) Cyanide of formula (VII).

The reaction procedure, workup and isolation of the reaction products of the formula (Ic) is carried out according to generally customary procedures.

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and especially as weed killers. Weeds in the broadest sense are all plants that grow in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides essentially depends on the amount used.

The active compounds of the invention may e.g. used in the following plants:

Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Impomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa , Rotala, Lindeernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.

Dicotyledonous cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocotyledonous cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Seeale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.

The compounds are suitable depending on the concentration for total weed control z. B. on industrial and railway tracks and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops, z. As forestry, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, gum, oil palm, cocoa, berry fruit and hop plants and for selective weed control in annual crops are used , .

In this case, the active compounds according to the invention can be used with particularly good success for the selective control of dicotyledonous weeds in monocotyledonous crops such as maize, wheat or barley. At appropriate application rates, the active compounds according to the invention moreover have insecticidal and growth-regulating activities.

The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, active-ingredient-impregnated natural and synthetic substances and superfine encapsulations in polymeric substances. These formulations are prepared in a known manner, for. Example, by mixing the active compounds with extenders, that is liquid solvents and / or solid carriers, optionally with the use of surfactants, emulsifiers and / or dispersants and / or foam-forming agents.

In the case of using water as an extender z. As well as organic solvents can be used as auxiliary solvent. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for. As petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones ^ ie acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

Suitable solid carriers are:

For example, ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates, as solid carriers for granules are: z. Broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and / or foam-producing agents are in question: z. Nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.

Adhesives ₍ such as carbonylmethyl cellulose, natural and synthetic powdery, granular or latex polymers such as gum arabic, polyvinyl alcohol, polyvinyl acetate, as well as natural phospholipids such as cephalins and lecithins, and synthetic phospholipids may be used in the formulations.) Other additives may be mineral and vegetable oils.

_Colorants} as inorganic pigments, for. For example, iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and Metallphthalocyaninfarbstoffe and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc are used.

The formulations generally contain between 0.1 and 95% by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such or in their formulations also in mixture with known herbicides for controlling weeds, ready-to-use formulations or tank mixes being possible.

For the mixtures known herbicides ^ such. 1-amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2,4 (1H, 3H) -

dione or N- (2-benzthiazolyl) -N, N'-dimethylurea for weed control in cereals; 4-Amino-3-methyl-6-phenyl-1,2,4-triazine-5 (4H) -one for weed control in sugar beet and 4-amino-6- (1,1-dimethylethyl) -3-methylthio-1, 2,4-triazine-5 (4H) -one for weed control in soybeans, in question. Also, mixtures with N, N-dimethyl-N '- (3-chloro-4-methylphenyl) -Rharstoff; N, N-dimethyl-N '- (4-isopropylphenyl) urea; 4-amino-6-t-butyl-3-ethylthio-1,2,4-triazin-5 (4H) -one; 2,4-dichlorophenoxyacetic acid; 2,4-dichlorophenoxypropionic acid; (2-methyl-4-chlorophenoxy) acetic acid; (4-chloro-2-methylphenoxyl-propionic acid; chloroacetic acid N- (methoxymethyl) -2,6-diethylanilide; 2-ethyl-6-methyl-N- (1-methyl-2-methoxyethyl) -chloroacetanilide; 2-) 4- (3,5-dichloropyrid-2-yloxy) -phenoxy] -propionic acid (2-benzyloxyethyl ester), (trimethylsilylmethyl ester) or - (2,2-diethoxyethyl ester), methyl-5- (2,4-dichlorophenoxy) - 2-nitrobenzoate; 3,5-diiodo-4-hydroxybenzonitrile; 3-isopropyl-2,1,3-benzothiadiazin-4-one-2,2-dioxide; 2-chloro-N - {[(4-methoxy-6 -methyl-1,3,5-triazin-2-yl) -amino] -carbonyl} -benzenesulfonamide; 4-ethylamino-2-t-butylamino-6-methylthio-s-triazine; N-methyl-2- (1 , 3-benzthiazol-2-yloxy) -acetamide; 1-N-di-n-propyl-thiocarbamic acid S-ethyl ester; N, N-diisopropyl-S- (2,3,3-trichloroallyl) -thiolcarbamate; N- (1-ethyl-propyl) -3,4-dimethyl-2,6-dinitroaniline; 2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine; 2-chloro-4-ethylamino-6- (3 -cyanopropylamino) -1,3,5 ^ triazine; 3,5-dibromo-4-hydroxybenzonitrile; [(4-amino-3,5-dichloro-6-fluoro-2-pyridyl) -oxy] -acetic acid or 1-methylheptyl esters are g if appropriate, an advantage. Surprisingly, some mixtures also show a synergistic effect.

A mixture with other known active ingredients, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and Bodenstrukturverbesserungsmittein is possible.

The active compounds can be used as such, in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The application is done in the usual way, for. B. by pouring, spraying, spraying, spreading.

The active compounds according to the invention can be applied both before and after emergence of the plants.

They can also be incorporated into the soil before sowing.

The amount of active ingredient used can vary within a substantial range. It depends essentially on the type of effect desired. In general, the application rates are between 0.01 and 10 kg of active ingredient per hectare of soil, preferably between 0.05 and 5 kg per ha.

The preparation and the use of the active compounds according to the invention are evident from the following examples.

Production Examples Example 1

CN -

(Method [a-a])

34 g (0.088 mol) of 5-bromo-4-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole are dissolved in 300 ml of absolute ether and concentrated at -78 ° C. under a nitrogen atmosphere of 60 ml ( 0.098 mol) of 15% n-butyllithium in hexane. The mixture is stirred for 2 hours at -78 ⁰ C, then initiates at -78 ⁰ C excess of gaseous carbon dioxide and slowly warmed to room temperature. For workup, the reaction mixture is mixed with 200 ml of water and washed twice with ether.

The aqueous phase is acidified with ice cooling, extracted three times with methylene chloride, the combined organic phases dried over magnesium sulfate and concentrated in vacuo. The residue crystallizes on trituration

Petroleum ether. ,

This gives 25 g (81% of theory) of 5-carboxy-4-cyano-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole of melting point 155-158 ⁰ C.

Example 2:

(Method [(a-ß)]

1.7 g (0.005 mol) of 5-methyl-4-nitro-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole are dissolved in a solution of 50 ml of water and 4 ml of 10% potassium hydroxide solution; with simultaneous introduction of atmospheric oxygen is added in portions 3.6 g (0.023 mol) of potassium permanganate and then heated to reflux temperature. The cooled reaction mixture is underlaid with methylene chloride, carefully acidified with 2N hydrochloric acid while cooling with ice and the precipitated manganese dioxide is reduced by sodium hydrogen sulfite addition. The organic phase is separated and extracted with saturated sodium bicarbonate solution. The basic extracts are acidified, extracted several times with methylene chloride, the combined organic extracts dried over magnesium sulfate and concentrated in vacuo.

This gives 0.34 g (18% of theory) of 5-carboxy-4-nitro-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole of melting point 102 ⁰ C (decomposition).

Example 3:

OOH

CF ₃

(Method [a-γ])

15 g (0.0045 mol) of 5-hydroxy-4-nitro-1- (2-chloro-4-trifluoromethyl-phenyl) -pyridazin-6-one are in 150 ml of 2% sodium hydroxide solution for 5 minutes at 80 ⁰ C and then 3 Minutes heated to 100 ⁰ C. The mixture is allowed to cool to room temperature, filtered the Niederschalgab, acidified the filtrate with ice cooling with 2N hydrochloric acid, extracted three times with 150 ml of methylene chloride, the methylene chloride phases dried over magnesium sulfate and the solvent removed in vacuo.

This gives 11 g (73% of theory) of 5-carboxy-4-nitro-1- (2-chloro-4-trifluoromethyl-phenyl) -pyrazole as an oily substance.

¹ H-NMR (CDCl ₃ ) δ = 8.34 ppm (3-pyrazole H)

Example 4

CO-OC ₂ H ₅

(Method [b-a])

3.5 g (0.01 mol) of 5-carboxy-4-cyano-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole are refluxed with 19 ml of thionyl chloride for 4 hours. The excess thionyl chloride is distilled off under reduced pressure, the residue treated with 15 ml of absolute ethanol and heated for 10 minutes at reflux temperature. The reaction mixture is concentrated in vacuo, the residue taken up in 50 ml of methylene chloride, washed twice with 25 ml of saturated sodium bicarbonate solution, dried over magnesium sulfate and concentrated in vacuo.

This gives 3.2 g (85% of theory) of 5-ethoxycarbonyl-4-cyano-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole of melting point 99-101 ⁰ C.

Example 5:

(Method [ba])

3.5 g (0.01 mol) of 5-carboxy-4-cyano-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole are refluxed with 10 ml of thionyl chloride for 2 hours. The excess thionyl chloride is distilled off under reduced pressure. The residue is treated at 1O ⁰ C with 30 ml of 25% aqueous ammonia and stirred for 10 minutes at room temperature. The reaction mixture is then extracted twice with 50 ml of methylene chloride, the organic phase washed with 30 ml of saturated sodium bicarbonate solution, dried over magnesium sulfate and concentrated in vacuo.

This gives 1.3 g (37% of theory) of 5-carbamoyl-4-cyano-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole of the melting point

Example 6:

(Method [b-a])

3.5 g (0.01 mol) of 5-carboxy-4-cyano-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole are refluxed with 15 ml of thionyl chloride for 2 hours. The excess thionyl chloride is distilled off under reduced pressure. The residue is dissolved in 20 ml of tetrahydrofuran, at 10 ⁰ C with 0.7 g (0.01 mol) of diethylamine and 0.8 g (0.01 mol) of pyridine and stirred for 1 hour at room temperature. Subsequently, the reaction mixture is poured into ice-water, extracted three times with 80 ml dichloromethane, the combined organic phases washed with saturated sodium bicarbonate solution, dried over magnesium sulfate and concentrated in vacuo.

This gives 2.7 g (67% of theory) of 5- (N, N-diethyl-carbamoyl) -4-cyano-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole of melting point 118-119 ⁰ C.

Example 7:

0-0-CH-CO-OC ₂ H ₅

(Method [b-a])

4.2 g (0.012 mol) of 5-carboxy-4-cyano-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole are refluxed with 20 ml of thionyl chloride for 2 hours. The excess thionyl chloride is distilled off under reduced pressure. The residue is dissolved in 15 ml of dimethoxyethane, treated with 1.4 g (0.012 mol) of ethyl lactate and 0.9 g (0.012 mol) of pyridine and stirred for 48 hours at room temperature and then for 48 hours at 75 ⁰ C. The reaction mixture is filtered, the filtrate is concentrated and the residue taken up in 100 ml of methylene chloride, washed with 30 ml of 2N hydrochloric acid and saturated sodium bicarbonate solution, dried over magnesium sulfate and concentrated in vacuo.

This gives 3.0 g (55% of theory) of 5- [1- (ethoxycarbonyl) -ethyloxycarbonyl] -4-cyano-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole as an oily substance.

¹ H-NMR (CDCl ₃ ) δ = 8.13 ppm (3-pyrazole H)

Example 8:

θ © 0-0 K

(Method [b-ß])

3.5 g (0.01 mol) of 5-carboxy-4-cyano-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole are titrated with 0.1 N aqueous potassium hydroxide solution. The aqueous solution is mixed with 50 ml of isopropanol and concentrated under reduced pressure to dryness.

This gives 3.6 g (93% of theory) of the potassium salt of 5-darboxy _: 4-cyano-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole of melting point 230 ⁰ C (decomposition) .-.

Example 9:

Cl

CN 0-0-CH-CO-OCH ₃

I ³

Cl CH ₃

CF,

(Method [b-y])

3.5 g (0.01 mol) of 5-carboxy-4-cyano-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole are dissolved in 50 ml of methyl ethyl ketone and mixed with 1.4 g (0.01 mol) Potassium carbonate added. The reaction mixture is heated under reflux until a white precipitate has formed. Thereafter, it is allowed to cool to room temperature, 2.0 g (0.012 mol) of α-bromopropionic acid is added dropwise, and it is stirred at 75 ° C for 3 hours. The reaction mixture is diluted with ether, filtered and the filtrate washed with 2% aqueous hydrochloric acid and saturated sodium bicarbonate solution, dried over magnesium sulfate and concentrated in vacuo.

This gives 2.2 g (50% of theory) of 5- [1- (methoxycarbonyl) -ethyloxycarbonyl] -4-cyano-1- (2,6-dichloro-4-trifluoromethylphenyl) pyrazole of melting point 88 ° C.

Example 10:

(Method [c-a])

3.3 g (0.01 mol) of 5-chloro-4-nitro-1- (2,4,6-trichlorophenyl) pyrazole and 6.0 g (0.02 mol) of tetrabutylammonium cyanide are added in 100 ml of toluene for 48 hours Room temperature stirred. For working up, it is washed several times with water, dried over sodium sulfate, concentrated by evaporation in a vacuum, and the oily crude product is purified by chromatography (silica gel, eluent: chloroform / acetone 9: 1).

This gives 1.5 g (47% of theory) of 5-cyano-4-nitro-1- (2,4,6-trichlorophenyl) pyrazole of melting point 143 ° C.

In a corresponding manner and in accordance with the general information on the preparation, the following 1-arylpyrazoles of the general formula (I) are obtained:

Ar

Table 2

Ex.

No. X

12 CN

Ar

Melting point / ⁰ C

Cl

11 CN -COOH

Cl

θ Θ -COO Na

Cl Cl

13 CN -COO Η, Ν CH (CHo)

w * 3

14 CN -C0-N (CH _{3) 2}

15 CN -CO-NH-C ₂ H ₅

145-148

260-263 (Zers.)

156-162

Cl Cl

CF-, 102-105

Cl Cl

131-135

Cl Cl

16 CN -CO-NH-CHr 17 CN -COOCH-18 CN -COOCH (CH ₃ ) ₂

19 NO

θ θ -COO Na

CF-, 189-193

Cl Cl

Cl Cl

160-164

CFo 80-85

Cl Cl

V- CF,

173 (Zers.)

Table 2 (cont

Ex.

No. X R Ar

Melting point / ⁰ C

20 NO

21 NO

-COOC ₂ H ₅ - -COOCH ₃ oil

22 NO ₂ -COO (CH ₂ ) ₂ CH ₃ 23 NO ₂ -C00CH (CH ₃ ) ₂ 24 NO ₂ -CO-N (C ₂ Hg) ₂ 25 NO ₂ -CO-NH-C ₂ H ₅ 26 NO ₂ -CO-NH- (CH ₂ ) 3 -CH ₃ 27 NO ₂ -COOC ₂ H ₅ -

Cl Cl

Cfo

CF ₃ 108-110

CF ₃ 62-66

CFq oil

Cl Cl

28 CN

-CO-O (CH ₂ ) ₂ -OCH ₃ - <" ^N ) -CF ₃ -63-68

Cl

Table 2 (continued) ·

Example

 No.

Ar

Melting point / ⁰ C

CN

-CO-SCH ₃

CH-

30 NO

2 -CO-O-CH-COOC ₂ H ₅

NO-

θ θ -COO Na

32 NO ₂ -CO-O- (CH ₂ ) ₂ ^{CH (CH} 3) 2

NO-

NO

2 -CO-O- (CH ₂ ) ₂ OCH ₃

35 NO ₂ -CO-O-CH ₂ CH = CH ₂ 36 NO ₂ -CO-O- (CH ₂ ) ₂ SCH ₃ - / V CF. oil

Table 2 (continued)

Example No. X R

Ar.

Schmel z point / ⁰ C

NO

NO ₂ -CO-O-CH-COOC ₂ H ₅

NO-

CN

CF

96-98

NO ₇ -CO-O-CH ₂ - ¹ COOC ₄ H ₉

Preparation of Starting Compounds Example 11-1:

35 g (0.109 mol) of 5-amino-4-cyano-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole in 137 ml (1.54 mol) of bromoform are added dropwise with stirring within 10 minutes with 38 ml (0.32 mol) of t-butyl nitrite, wherein the temperature of the reaction mixture increases to 75 ° C. After completion of the addition, the mixture is stirred for a further hour at reflux temperature, the mixture is concentrated in vacuo and the residual oil is purified by column chromatography (silica gel, eluent: methylene chloride).

This gives 29 g (69% of theory) of 5-bromo-4-cyano-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole of melting point 92 ⁰ C. In a corresponding manner and according to the general information for Preparation to obtain the following 5-halo-1-arylpyrazoles of the general formula (II):

shark

Tabel le 3 Ex. No. X

Hal

Ar

Melting point / ⁰ C

II-2 CN Br

CF ₃ 127

II-3 NO ₂ Br

Example 1I1-1:

CF ₃ 96

5 g (0.0147 mol) of 4-carboxy-5-methyl-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole are dissolved in 36 ml of concentrated hydrochloric acid. 3.8 ml (0.0394 mol) of 98% nitric acid are added dropwise, the mixture is heated at 120 ° C. for 1 hour and then allowed to cool. The reaction mixture is added to ice-water, extracted with methylene chloride, the methylene chloride phases washed with saturated sodium bicarbonate solution, dried over magnesium sulfate and concentrated in vacuo.

This gives 3.7 g (74% of theory) of 5-methyl-4-nitro-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole of the melting point

91-92 ⁰ C.

Example XIX-1:

CF ₃

3.7 g (0.01 mol) of 4-ethoxycarbonyl-5-methyl-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole are heated to 120-125 ⁰ C in 40 ml of hydrobromic acid for 48 hours, the resulting ethanol is distilled off simultaneously. Subsequently, the excess hydrobromic acid is distilled off, the residue taken up in methylene chloride and washed with saturated sodium bicarbonate solution. The organic phase is dried over magnesium sulfate and concentrated in vacuo

 This gives 2.0 g (67% of theory) of 5-methyl-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole of melting point 78-84 ° C.

Correspondingly, Example XIX-2 is obtained:

CF ₃

Melting point 45-47 ⁰ C. Example XVIII A-1:

0OH

8.7 g (0.0237 mol) of 4-ethoxycarbonyl-5-methyl-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole are dissolved in a solution of 50 ml of ethanol, 1.5 g (0.0375 mol ) Sodium hydroxide and 25 ml of water and stirred for 48 hours at room temperature. The reaction mixture is washed with methylene chloride and the alkaline phase is acidified under ice-cooling with 2N hydrochloric acid. It is then extracted with methylene chloride, the methylene chloride phase dried over magnesium sulfate and concentrated in vacuo.

This gives 8 g (100% of theory) of 4-carboxy-5-methyl-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole of the melting point

In corresponding manner one obtains

Example XVIII a-2:

OOH

Melting point 161-162 ⁰ C. Example XVIII-I:

COOC ₂ H ₅

5 g (0.013 mol) of N- [2-ethoxycarbonyl-2-acetyl-vinyl] -N '- (2,6-dichloro-4-trifluoromethyl-phenyl) -hydrazine are dissolved in 50 ml of ethanol, treated with 1 ml of concentrated sulfuric acid and Heated under reflux for 1 hour. The reaction mixture is concentrated in vacuo, taken up in methylene chloride, washed with saturated sodium bicarbonate solution, the methylene chloride phase dried over magnesium sulfate and concentrated in vacuo.

This gives 4.1 g (86% of theory) of 4-ethoxycarbonyl-4-methyl-1- (2,6-dichloro-4-trifluoromethyl-phenyl) -pyrazole of melting point 61-62 ⁰ C.

In a similar manner gives Example XVIII-2

'COOC ₂ H ₅

Melting point 69-70 ⁰ C

Example XVII-I:

-NH-CH = C <

COOC ₂ H ₅

CO Chg

12.25 g (0.05 mol) of 2,6-dichloro-4-trifluoromethylphenylhydrazine in 25 ml of diethyl ether are added dropwise at 0 ° C. to a solution of 9.3 g (0.5 mol) of ethyl ethoxymethyleneacetacetate in 50 ml of diethyl ether. After complete addition, the mixture is stirred for a further hour at room temperature and then concentrated in vacuo. This gives 19 g (100% of theory) of N- [2-ethoxycarbonyl-2-acetyl-vinyl] -N '- (2,6-dichloro-4-trifluoromethylphenyl) hydrazine of melting point 75-76 ° C.

Example IV-1:

Cl

CF ₃

31 g (0.09 mol) of 4,5-dichloro-1- (2-chloro-4-trifluoromethylphenyl) -pyridazin-6-one are dissolved in 100 ml of dimethylformamide. To. This mixture is allowed to drop at 105 ⁰ C, a solution of 31.7 g (0.46 mol) of sodium nitrite in 32 ml of water and stirred for a further hour stirring at reflux temperature. After cooling, it is quenched with water, acidified with 2N hydrochloric acid under ice-cooling and extracted twice with methylene chloride. The combined organic phases are dried over magnesium sulfate and concentrated in vacuo.

Trituration with ethanol gives 18.4 g (61% of theory) of 5-hydroxy-4-nitro-1- (2-chloro-4-trifluoromethyl-phenyl) -pyridazin-6-one of melting point 213 ° C.

In a corresponding manner, Example IV-2 is obtained:

Melting point 180 ° C (decomp.)

Example XXIM: Cl

105 g (0.29 mol) of mucochloric acid (2-chloro-4-trifluoromethylphenyl) hydrazone are dissolved in 500 ml of glacial acetic acid and heated under reflux for 1 hour. The still hot solution is mixed with a little water to accelerate the crystallization. The precipitate is filtered off with suction and triturated with petroleum ether.

This gives 72 g (72% of theory) of 4,5-dichloro-1- (2-chloro-4-trifluoromethyl-phenyl) -pyridazin-6-one of melting point 183 to

In a corresponding manner, example XXII-2 is obtained:

Melting point 177 ⁰ C. Example XMM:

Cl Cl

Cl

HOOC-

105.3 g (0.5 mol) of 2-chloro-4-trifluoromethylphenylhydrazine are dissolved in 500 ml of toluene, mixed at room temperature with 84.5 g (0.5 mol) of mucochloric acid and stirred for 2 hours at room temperature.

By suction and drying of the crystalline precipitate obtained 180g (100% derTheorie) to Mucochlorsäure- (2-chloro-4-trifluoromethyl-phenyl) hydrazone of melting point 176 ⁰ C.

In a corresponding manner, Example XXI-2 is obtained:

Cl Cl Cl

I i

HOOC-CzZC-CH = N-N

Cl

Melting point 154-155 ⁰ C

applications

In the following application examples, the compound shown below was used as the reference substance: 'CN

Cl

4-cyano-5-propionamido-1- (2,4 / 6-trichlorophenyl) pyrazole (known from DE-OS 3226513)

Example A

Pre-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Seeds of the test plants are sown in normal soil and watered after 24 hours with the preparation of active ingredient.

It is advisable to keep the amount of water per unit area expediently constant. The concentration of active ingredient in the preparation does not matter, only the application rate of the active ingredient per unit area is decisive. After three weeks, the degree of damage of the plants is rated in% damage in comparison to the development of the untreated control. It means:

0% = no effect (as untreated control) 100% = total destruction

A clear superiority in the crop selectivity, especially in corn, compared to the reference substance show in this test z. B. the compounds according to the preparation examples: 1,3,8 and 20

Example B

Post-emergence test

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

With the preparation of active compound is injected test plants, which have a height of 5-15cm so that the respective desired amounts of active ingredient per unit area are applied. The concentration of the spray mixture is chosen so that in 2000I water / ha, the respective desired amounts of active ingredient are applied. After three weeks, the degree of damage of the plants is rated in% damage in comparison to the development of the untreated control.

It means:

0% = no effect (as untreated control) 100% = total destruction

A clear superiority in the crop selectivity, especially in wheat and barley, compared to the reference substance (A) show in this test z. B. the compounds according to Preparation Examples 2, 20 and 21

Claims (6)

in which X is cyano or nitro, R is cyano or a residual CO-YR ¹ , Y is oxygen, sulfur or a residual N- R ² stands, R ^{1 is} hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkenyl, haloalkenyl, alkynyl or each optionally substituted cycloalkyl, aralkyl or aryl, a radical O U 10 C-Z-R 11 stands, or R ^r in the case where Y represents oxygen, sulfur or an ReSt-N-SO ₂ -R ^3, is also a salt-bound inorganic or organic cation, R ^{2 is} hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkenyl, alkynyl or haloalkenyl; each is optionally substituted cycloalkyl, aralkyl or aryl, or is a radical SO ₂ -R ³ , where "~ Each R ³ is optionally substituted alkyl, aralkyl or aryl, R ¹⁰ and R ^{12 are} independently hydrogen or alkyl, R ^{11 is} hydrogen, alkyl, alkenyl or alkynyl, Z is oxygen, sulfur or N-alkyl and m is a number 1,2,3,4,5 or 6, and Ar for a rest or for a rest 8th. stands, in which R ^{4 is} cyano, nitro, halogen, alkyl, alkoxy, alkoxycarbonyl, haloalkyl, haloalkoxy or an ReSt-S (O) _n -R ⁹ , R ⁵ , R ⁶ , R ⁷ and R ^{8 are} independently hydrogen, cyano, nitro, halo, alkyl, alkoxy, alkoxycarbonyl, haloalkyl, haloalkoxy or a radical S (O) _n -R ⁹ , wherein R ^{9 is} alkyl, haloalkyl, amino, alkylamino or dialkylamino, and η is an integer O, 1 or 2, in addition to extenders and / or surface-active substances. 2. Composition according to claim 1, characterized in that in the formula (I) X is cyano or nitro, R is cyano or a radical -CO-YR ¹ , Y is oxygen, sulfur or a residual N-position, R ² . R ^{1 is} hydrogen, straight-chain or branched alkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkenyl, haloalkenyl or alkynyl each having up to 12 carbon atoms and in the case of haloalkyl and haloalkenyl having in each case 1 to the same or different halogen atoms, for cycloalkyl having 3 to 7 C 1 -C 4 or each optionally mono- or polysubstituted, identically or differently, by halogen, cyano, nitro and in each case straight-chain or branched alkyl, alkoxy, alkylthio or haloalkyl having in each case 1 to 4 carbon atoms and in the case of the haloalkyl having 1 to the same or different halogen atoms Phenyl, benzyl or phenethyl, as well as a radical stands,
m and also R ¹ for the case that Y is oxygen, sulfur or a ReSt-N-SO ₂ -R ³ , also for one equivalent of an alkali, alkaline earth, copper, zinc, manganese, tin, iron -, cobalt or nickel cations or an optionally mono- or polysubstituted, identically or differently substituted ammonium, phosphonium or Sulfoniumkations, where as substituents in question are: straight-chain or branched alkyl having 1 to 18 carbon atoms, phenyl or benzyl; R ^{2 is} hydrogen, in each case straight-chain or branched alkyl, hydroxyalkyl, alkoxyalkyl, alkylthioalkyl, haloalkyl, alkenyl, haloalkenyl or alkynyl having in each case up to 12 carbon atoms and in the case of the haloalkyl or haloalkenyl having 1 to 15 identical or different halogen atoms, for cycloalkyl with 3 to 7 carbon atoms or, if appropriate, singly or multiply, identically or differently, by halogen, cyano, nitro and in each case straight-chain or branched alkyl, alkoxy, alkylthio or haloalkyl having in each case 1 to 4 carbon atoms and in the case of the haloalkyl having 1 to 9 or phenyl substituted by different halogen atoms, benzyl or phenethyl, furthermore represents a ReSt-SO ₂ -R ³ ,
in which R ^{3 is} in each case straight-chain or branched alkyl or haloalkyl having in each case 1 to 6 carbon atoms and in the case of the haloalkyl having 1 to 9 identical or different halogen atoms or optionally mono- or polysubstituted by identical or different substituents, phenyl, benzyl or phenylethyl, where as substituents in each case: halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy, alkylthio or halogenoalkyl having in each case 1 to 4 carbon atoms and in the case of the haloalkyl having 1 to the same or different halogen atoms; and R ¹⁰ and R ¹² independently of one another each represent hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms, R ¹¹ is hydrogen or each straight-chain or branched alkyl, alkenyl or alkynyl having in each case up to 6 carbon atoms, Z is oxygen, sulfur or an NC _r C ₄ alkyl radical and m is a number 1, 2, 3, _4, 5 or 6, Ar for a rest or for a rest stands, R ^{4 is} cyano, nitro, halo, for each straight chain or branched alkyl, alkoxy, alkoxycarbonyl each having 1 to 4 carbon atoms, each represents straight or branched haloalkyl or haloalkoxy each having 1 to 4 carbon atoms and 1 to 9 same or different halogen atoms or for a ReSt-S (O) _n -R ⁹ stands, R ⁵ 'R ⁶ , R ⁷ and R ^{8 are} independently hydrogen, cyano, nitro, halogen, each being straight or branched alkyl, alkoxy or alkoxycarbonyl each having 1 to 4 carbon atoms, each being straight or branched haloalkyl or haloalkoxy each having 1 to 4 carbon atoms and 1 to 9 are the same or different halogen atoms or a ReSt-S (O) _n -R ⁹ , wherein R ^{9 is} amino, in each case straight-chain or branched alkyl, alkylamino, dialkylamino or haloalkyl having in each case 1 to 4 carbon atoms in the individual alkyl moieties and in the case of the haloalkyl having 1 to 9 identical or different halogen atoms, η is an integer O, 1 or 2. 3. Composition according to claim 1, characterized in that in the formula (I) X is cyano or nitro, R is cyano or a residual CO-YR ¹ , wherein
Y is oxygen, sulfur or a residual N- stands,
R ^{1 is} hydrogen, optionally mono- to trisubstituted, identical or different, by fluorine, chlorine, hydroxyl, methoxy, Ethoxy, methylthio or ethylthio substituted methyl, ethyl, η- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, for optionally mono- to trisubstituted by identical or different fluorine or chlorine-substituted allyl, propenyl or Butenyl, for propargyl, propynyl, butynyl or pentynyl, for cyclopropyl, cyclopentyl, cyclohexyl, for the sake of optionally one to five times, identically or differently, by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, Methoxy, ethoxy, methylthio or trifluoromethyl substituted benzyl or phenyl, furthermore a radical -ZR ¹¹ stands, and moreover, in the event that Y is oxygen, sulfur or a ReSt-N-SO ₂ -R ³ , also for one equivalent of a sodium, potassium, magnesium, calcium, barium, copper, zinc , Manganese, tin, iron, Cobalt or nickel cations or an optionally mono- to trisubstituted by identical or different methyl, ethyl, n- or or i-propyl, n-, i-, s-tert-butyl, benzyl or phenyl-substituted ammonium, phosphonium or sulfonium cation
stands, R ^{2 is} hydrogen, optionally ¹ to 3 times, the same or different by fluorine, chlorine,. Hydroxy, methoxy, ethoxy, methylthio. or ethylthio is substituted methyl, ethyl, η- or i-propyl, n-, i-, s-tert-butyl, n- or i-pentyl, optionally mono- to trisubstituted, identically or differently, by fluorine or chlorine-substituted allyl propenyl or butenylpropargyl, Propinyl, butynyl or pentynyl, cyclopropyl, cyclopentyl, cyclophexyl, in each case optionally one to five times, identically or differently, benzyl or phenyl substituted by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, methoxy, ethoxy, methylthio or trifluoromethyl, and also for a rest -SO ₂ -R ³ stands, where R ^{3 is} methyl, ethyl, η- or i-propyl, n-, i-, s- or tert-butyl or optionally one to five times, identically or differently by fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl , Methoxy, methylthio or trifluoromethyl substituted benzyl or phenyl, R ¹⁰ and R ¹² are each independently hydrogen, methyl, ethyl, η- or i-propyl, R ^{11 is} hydrogen, methyl, ethyl, η- or i-propyl, n-, i-, s- or tert-butyl, for allyl. Propenyl, butenyl, propargyl, propynyl or butynyl, Z is oxygen, sulfur, an N-methyl radical or an N-ethyl radical and m is a number 1, 2, 3 or 4, Ar for a rest or for a rest stands, R ^{4 is} cyano, nitro, fluoro, chloro, bromo, methyl, ethyl, η- or i-propyl, methoxy, ethoxy, trifluoromethyltrichloromethyl-dichlorofluoromethyl, chloromethyl, dichloromethyl, difluoromethyltetafluoroethyl, tetrafluoromethyl, trifluorodichloroethyl, trifluorodichloroethyl , Pentachloroethyl, trifluoromethoxy, trichloromethoxy, dichlorofluoromethoxy, difluorochloromethoxy, chloromethoxy, dichloromethoxy, difluoromethoxy, pentafluoroethoxytetrafluoroethoxy, trifluorochloroethoxy, trifluoroethoxy, difluorodichloroethoxy, trifluorodichloroethoxy, pentachloroethoxy, or a ReSt-S (O) _n -R ⁹ ; R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently hydrogen, cyano, nitro, fluoro, chloro, bromo, methyl, ethyl, η- or i -propyl, n-, i-, s-tert-butyl, methoxy , ethoxy, trifluoromethyl, trichloromethyl, dichlorofluoromethyl, difluorochloromethyl, chloromethyl, dichloromethyl, difluoromethyl ^ entafluormethyMetrafluorethyMrifluorchlorethyMrifluorethyl, DiflourdichlorethyMrifluordichlorethyl ^ entachlorethyl ^ ürTrifluormethoxy, trichloromethoxy, dichlorofluoromethoxy, difluorochloromethoxy, chloromethoxy, dichloromethoxy, difluoromethoxy, pentafluoroethoxy ^ etrafluorethoxy ^ rifluorchiorethoxyjTrifluorethoxy, Difluordichlorethoxy, Trifluordichlorethoxy, Pentachlorethoxy or a ReSt-S (O) _n -R ⁹ , where R ^{9 is} amino, methylamino, ethylamino, dimethylamino, diethylamino, fluorodichloromethyl, difluoromethyl, tetrafluoroethyl, trifluorochloroethyl, rifluoromethyl, methyl or ethyl, η is a number 0,1 or 2. 4. A method for controlling weeds, characterized in that 1-aryl-pyrazoles of formula (I) according to claims 1 to 3 act on weeds and / or their habitat. 5. Use of 1-aryl-pyrazoles of the formula (I) according to claims 1 to 3, characterized in that they are used for controlling weeds. 6. A process for the preparation of herbicidal agents, characterized in that mixing 1-arylpyrazoles of the formula (I) according to claims 1 to 3 with extenders and / or surface-active substances.