DD149152A5 - HERBICIDE MEDIUM - Google Patents

Abstract

Substituted Phenoxialkancarbonsaeurederivate of formula I, wherein R is halogen, CF & ind3 !, NO & ind2 !, CN, NH &sub2;, alkyl, alkoxy, alkylthio or (substituted) phenoxy; n is a number from 0 to 4; A is O, S, NH or N-alkyl; X -CH- or -CH & ind2! CH & ind2! -; R & ind1! Alkyl or (substituted) phenyl and Z represents a carboxy, carboxylic ester, carbonamide, carbohydrazide, thioamide, nitrile, hydroxymethyl, acyloxymethyl or sulphonyloxymethyl group, are effective herbicides, in particular against monocotyledonous harmful plants.

Description

The invention relates to herbicidal Llittel for the selective weed control in agriculture.

Characteristic of the known technical solutions

^A British Patent 1,157,558 already discloses compounds of the formula I in which Z represents various arbonamido and carbanilidoreotes (not claimed herein). The compounds of this patent possess vasodilatory properties; herbicidal treatment is not reported by them. However, experiments have shown that these compounds also have a certain herbicidal activity.

Z iel the invention

The aim of the invention is the provision of .littein with improved herbicidal V / rekung, broad selectivity spectrum and good plant compatibility.

Explanation of the reading of the invention

The invention has for its object to find new Phenoxialkancarbonsäurederivate having strong herbicidal properties and are suitable as.Wirkstoff in herbicidal compositions.

η, ι · 'μ in -', '·

219 199

9.6,1980

AP C 07 D / 219 199

56 900/12

According to the present invention, novel heterocyclically substituted Phenoxialkancarbonsäurederivate of general formula I

C-X-

(D

found,

wherein

R is halogen, CF ₃ , UO ₂ , CIJ, Td ₂ , (C ₁ -C ₄ -alkyl), (C ₁ -C ₄ ) -alkoxy, (C ₁ -C ₄ ) -alkylthio or phenoxy, which may optionally be to three times by halogen, CP ^, (C ₁ -C J-alkyl, IiO ₂ or the group HH-C (O) -R ₂ may be substituted;

η 0, 1, 2, 3 or 4,

A is O, S, NH or U- (C ₁ -C) -alkyl,

X is -CH ₂ - or -CH ₂ -CII ₂ -, R _{1 is} H or (C ₁ -C ₄ ) -alkyl, Z is a group of the formula

O η -C-OR, i f 0 0 Il "-C-S-R ^, -C-NH-R OR / - τ>, -CNN ⁸ , ^R 7 possibly S -C -NH ₂ , CN, -CH ₂ O, ι, 0 -CH ₂ -OCR ₉ or -CH ₂ -O-SO-! R _5: H, (C i-CIJ alkyl, the through 1 - 6

Halogen, preferably F, Cl, Br and / or by OH, '(C ₁ -Cc) -alkoxy, (C ₁ -C ₄ ) -alkylthio, (C ₁ -Cc) -alkoxy (C ₂ -C ₀ ) alkoxy, HaloCn- (C ₁ -C ₂ ) alkoxy, methoxy-dioxi-ethoxy, (C ₁ -C ₄ ) -alkylamino, di- (C ₁ -C ₄ ) -alkylamino, (C ₁ -C ₄ ) -alko icarbonyl, phenyl, oxiranyl and phenoxy, the latter also being substituted

¹ ^ to ^ zv / eifach by halogen or (C ₁ -C ₄ ) alkyl

may be substituted;

(C _D -C _C) -cycloalkyl or halo- (C ₅ -C ₀₎ alkyl; (C _s -C _c) alkenyl, halo (C ₃ -C ₆₎ alkenyl or (C ₀ -C ₀₎ cycloalkenyl;

(C ₅ -C ₄ ) -alkynyl which is optionally monosubstituted or partially substituted by (C ₁ -C ₆ ) -alkyl, phenyl, halogen or (C ₁ -C ₂ ) -alkoxy; Phenyl which is optionally mono- to trisubstituted by (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ ) -alkoxy, halogen, NO ₂ or

² ^ CF _{5 is} substituted; Furfuryl, tetrahydrofurfuryl or

a cation equivalent of an organic or inorganic base;

^R4: (C ₁ -C ₆₎ -alkyl which is optionally substituted by (C ₁ -C ₄₎ -30

Alkoxi, halogen or phenyl is substituted, the latter may also be mono- to trisubstituted by (C ₁ -C ₄ ) alkyl and halogen;

219 199

-3- 9.6.1980

AP C 07 D / 219 199 56 900/12

(C 1 -C 6) -alkenyl or phenyl which is optionally monosubstituted to trisubstituted by (C 1 -C 4) -alkyl and / or halogen,

H, (C ₁ -C ₆ M -cyclo, hydroxy (C ₁ -C ₆ ) -alkyl or (C ₅ -C ₆ ) -cycloalkyl, H or CH ₃ , H, CH ₃ or C ₃ H ₅ ,

R _{8 is} H, CH ₃ , C ₂ H ₅ or phenyl,

R ₁ (C ₁ -C 9) -alkyl, which is optionally monosubstituted to trisubstituted by halogen, C ₃ -, C ₅ - or C ₆ -cycloalkyl, (C ₃ -C ₆ ) -alkenyl, phenyl, (C ₁ -C.) - Alkylphenyl, (Cj-Cj-alkoxiphenyl, halophenyl, ^ rifluoromethylphenyl or nitrophenyl and

R _{1 is} Q (C .. -C.) -Allcyl or phenyl which is optionally substituted by one to three times by halogen, CP ₃ , IiC ₂ or (C ₁ -C) alkyl.

The compounds of the formula I are valuable herbicides with particular activity against grass weeds <>

The in the racks R ₁ - R; R and R listed alkyl, alkenyl or alkynyl radicals may be both straight-chain and branched.

Preferred compounds of the general formula I are those in which

R t is halogen, (C -C) -alkyl

ι tL

η: 0, 1 or 2 10

A: 0, S, N- (C _t -C ^) - alkyl, X: - ^CH ~ p ^{or CH} 2 ^'CH 2 R ** .: H or CH

Zi is a group of the formula

0 "°, R S

-COR ₃ , -CN ^ ⁵ , -CNH ₂ or -CN

R ~: H, (C -Co.) -Alkyl which gege Bono if durcli halogen, (C ..- C / -) -alkoxy is substituted; or a cation equivalent of an organic or inorganic base,

R: II or (C -C.) - Alkyl.

Particularly preferred compounds of general formula I are those in which

R t is chlorine, bromine.

η ί O ₁ 1

A: O, S

X:

R ₁ : -CH ₃

219 199

Z: -COOR

R: H _f (C -C) - represents alkyl, optionally substituted by (C -C) -alkoxy, Cl, Br, or an alkali or -Erdalkalikation.

The compounds of the general formula I can be prepared from starting materials known per se or prepared by known processes. These methods are characterized in that

a) compounds of the formula II

NH-

with compounds of the formula III,

(J) -OCH-Z '(III) wherein

Q may be a hydroxyl group, an alkoxy group or a halo of cenatoin, and Z 'is a lower alkoxycarbonyl;

b) compounds of the formula IV

with compounds of the formula V

V-CH-Z (V)

V is halogen or the radical of an aliphatic or aromatic sulfonic acid, is reacted;

c) compounds of formula I in which Z represents the -COOR_ group, hydrogenated and the resulting alcohols (z = CH-OH), if desired, by reaction with Carbonsäurcn, carboxylic acid halides or anhydrides in the

corresponding carboxylic acid ester - ", or

(Z = -CII ₂ -OCR ₉ )

converted by reaction with SuIfosäurehalogeniden in sulfonic acid ester (Z = -CH-O-SO ₂ -R);

d) compounds of the formula I in which Z is the -COOR, - group. represents (in which R "is not hydrogen) in known Veise in salts (Z = COOKat) or .. free acids (Z s GOOIl) transferred;

o) compounds of formula I ₁ in which Z represents the -C00R_ group, with ammonia, amines or hydrazines to acid amides (Z = CONII) or acid hydrazides

(Z s = -CO-N (R ^ jN )) ; 20. ^R 7

/·.·. f) compounds of the formula I ₁ in which Z represents the -COOLI group, converted by reaction to give acid halides and subsequent reaction with amines, hydrazines or alcohols in acid anides, acid hydrazides or esters ² →;

g) compounds of the formula I in which Z is a low molecular weight ester group, with alcohols of the formula

uniestert; 30 ^J ί

h) compounds of the formula I in which Z represents the -CO-NHg group, dehydrated and the resulting nitriles (ZS = CN), if desired, by addition of H ₂ S in the corresponding thioamides (Z = CS-NH ₂ ). ··

SI 9 199

For a), the free acid (Q Preferably = 0H) or the acid halide (Q = Cl) used Z'bedeutet -COOC _1-6 alkyl.

The reaction is carried out with or without solvent at temperatures of 100-200 ⁰ C. Preferred solvents are xylene, chlorobenzene, dichlorobenzene. The water formed in the reaction is distilled off.

To b) The reaction of compounds IV and V is preferably carried out in inert aprotic solvents such as aliphatic or aromatic hydrocarbons (v / ie, for example, benzene, toluene), acetonitrile, acetone, DMSO, DHF at temperatures between 50 ⁰ C and the boiling point of the solvent in Presence of bases such as carbonate, alkali or tertiary organic bases. V / is halogen or a sulfonic acid residue such as tosylate or mesylate.

,

To c) The reduction of acids or esters to alcohols is preferred with complex metal hydrides !! LiAlH _{4 was} carried out in ethereal, anhydrous solvents. Since the reaction is usually exothermic, there is generally no need for external temperature supply. The subsequent esterification with acid anhydrides or acid halides is carried out in inert solvents (as in a)) at temperatures between 0 ^° C. and the boiling point of the solvent with the addition of an organic or inorganic base, for example Na ₂ CO ₃ , K ₂ CO ₃ , pyridine or triethylamine , The esterification with carboxylic acids is carried out either by addition of water-binding agents vie P ₂ O ₅ or by azeotropic extractive distillation of the acidified components.

To e) For the reaction of esters of formula I with amines, ammonia or hydrazines are preferably used the same solvents as in b) and operates at temperatures between 40 ⁰ C and reflux temperature.

To £) The conversion of acids of formula I are in acid halides in a known manner. The same applies to the subsequent reaction with ammonia, amines or hydrazines. To bind the liberated hydrogen halide an at least one molar excess of the base used is required.

To g) The reaction is carried out by acidic or basic catalysis. The alcohol to be introduced into the ester is expediently added in excess and the liberated, lower-boiling alcohol is continuously distilled off to the extent that

20 in which it is formed in the transesterification.

To h) In the dehydration of amides to nitriles is vorzugsv / eise in aromatic hydrocarbons at temperatures of 50 ⁰ C to the boiling point. The subsequent addition of H ₂ S takes place zv / eckmäßigerweise in the autoclave in Gegenv / art catalytic amounts of a base (preferably ethanolamine) at temperatures between 50 and 150 ⁰ C.

The heterocyclic phenols of the formula IV required for the preparation of the compounds of the general formula I according to the invention can preferably be obtained by condensation of arainophenols, arninothiophenols and diaminobenzenes with 4-hydroxyphenylacetic acid or 3- (4'-

219 199 _.

Hydroxyphenyl) propionic acid. The condensation takes place while distilling off water at reaction temperatures of 120-200 C.

The compounds of general formula I according to the invention are very effective in the pre- and Xachauflaufverfahren against a wide range of monocotyledonous harmful plants, but at the same time they are excellently tolerated by dicotyledonous crops and some cereals.

The compounds are therefore u. a. suitable for the selective control of grass weeds in crops. The present invention therefore also herbicidal Mittcl, which are characterized in that they contain a "her-" bizid effective amount of a compound of general formula I in addition to conventional additives and Formierungshilfsmittcln.

The erfindungsgeraäßen agents contain the active ingredients of the formula I in general to 2 - 95 wt .- ^. They can be used in the customary formulations as wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules.

Wettable powders are preparations which are uniformly dispersible in water and which, in addition to the active substance except a diluent or inert substance, also contain wetting agents, e.g. polyoxethylated alkylphenols, polyoxethylated oleyl, stearylamines, alkyl or alkylphenylsulfonates and dispersants, e.g. lignosulfonic acid sodium, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, or also oleylmethyltaurine-containing sodium.

Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, e.g. butanol,

Cyclohexanone, Dimethylforrnamid, xylene or higher-boiling aromatics and addition of a nonionic wetting agent, such as a polyoxyethylated alkyl. phenols or a polyoxethylated oleyl or stearylamine.

Dusts are obtained by grinding the active ingredient with finely divided solid materials, e.g. Talc, natural clays such as kaolin, bentonite, pyrophyllite or diatomaceous earth.

Granules can be prepared either by Verdüscn of the active ingredient on adsorptive, granular Incrtmaterial or duch application of Wirkst of fkonzentraten by means of adhesives, eg. I). Polyvinyl alcohol, polyacrylic acid sodium, or mineral oils on the surface of carriers such as sand, kaolinite, or of granular Incrtmaterial. Also, suitable fertilizers may be prepared in the manner customary for the manufacture of fertilizer granules, if desired in admixture with fertilizers.

In the case of the herbicidal compositions, the concentrations of the active compounds in the commercial formulations can be determined by

Be parted. In wettable powders, the active ingredient varies concentration eg zv / een about 10 ° _(Ό and 95? ·>, The remainder being the above formulation additives. In emulsifiable concentrates, the active ingredient concentration is about 10 ^c / o to 80%. Dust-like formulations usually contain 5 - 20 ^c / o of active substance In the case of granules, the active substance depends, in part, on whether the active compound is liquid or solid and uses such granulating agents, fillers, etc.

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AP C 07 D / 219 199 56 900/12

For use, the commercial concentrates are optionally diluted in a conventional manner, for. B. with wettable powders and emulsifiable concentrates by means of V / asser. Dusty and granulated preparations as well as sprayed solutions are not diluted with other inert substances before use. With the external conditions such as temperature, humidity and. a, varies the required application rate _o It can vary within wide limits, z. B. between 0.05 and 10.0 kg / ha or more active substance, but it is preferably between 0.1 and 5 kg / ha.

The active compounds according to the invention can be combined with other herbicides, insecticides and fungicides.

embodiment

The invention is explained in more detail below with reference to some examples.

HERSTELLtJNGSBEISPIELE

Example 1 . ,

- (2'-benzothiazolyl-thyi) -phenoxy-7-propionic acid ethylisone

24.1 g (0.1 mol) of 4- (2'-benzthiazolylmethyl) phenol are mixed with 16.6 g, (0.12 mol) of potassium carbonate; and 19.9 g (0.11 mol) of 2-Brorapropionsäureethylester in 100 ml of acetonitrile for 8 hours under reflux. Inorganic salts are filtered off, acetonitrile is distilled off under reduced pressure "and the residue in a high vacuum (boiling point).

5 point 205 - 2C8

ΟΛ

0.07 bar) distilled. You get

50 g £ 88 # d.Th. ethyl 2- / 4 '- (2 "-benzothiazolylmethyl) phenoxlT-propionate.

CH ₃

Example 2

2- / ^l - (2 "-benzothiazolylmethyl) -phenoxy-7-propionic acid

54.1 (0.1 mole) 2- / 4 '- (2 "-benzothiazolylmethyl) -phenoxy, 7-

* . Propionic acid ethyl ester are stirred with 4.4 g (O _v ll MoI) sodium hydroxide 200 ml V / asser and 50 ml of methanol for 16 hours at room temperature. Subsequently, with 15 ml of conc. Hydrochloric acid and corresponds

219

standing precipitate filtered off and dried. 30 g ~ 96% of theory 2- / 4 '- (2 "-Benzothiazolylniethylen) -phenoxjT-propionic acid of melting point 154-156 ⁰ C.

V-CH,

CH ₃

-OCHCOOH

10. In an analogous way we obtain:

example

connection

according to example

Kp./Fp./n

CH ₃

-OCHCC ₂ CH ₃

CH ₂ - (Q) -OCHC C ₂ C ₂ H.

CH ₃

-OCHCO ₂ CH ₃

CH ₅

-OCHCOONa

CH ₃

-OCHCO ₂ C ₂ H ₅

Mp 63

Kp. 174-6. ⁰ C, 0.013 nibar

Mp 70

⁰ C

glassy, tough

example

Compounds according to;

kp

CH ₉

CH

-OCHCO ₂ CH ₃

Cl Cl

10

11

Cl

Bp 192 ^° C, 0.007 mbar

V ^cH2 "ö-CH ₃

OCHCO ₂ C ₂ H,

CH ₂

CH ₃

-OCHCO ₂ C ₂ H ₁

CH.

h: O ₂ Ch ₂ c H ₂ OCh ₃

"OCHCO ₂ CH ₂ Gi ₂ Cl

CH ₂ Gi ₂

14

OCH ₂ CO ₂ CH ₃

CH ₃

Bp. 181 ^° C, 0.005 mbar

Mp 91-93 ⁰ C

Kp .: 226 ⁰ C, .0,08 mbar

219 199

example

15

16

19

Compound> -0CHC0 ₂ C ₂ H ₅

CH ₃

V-CHpCH

₂ CH ₂

2 CH ₂

/ ~ ^CH 2 - CH

CH ₅

-OCHCO ₂ CH ₃

CH ₃

-OCHCO ₂ C ₂ H ₅

iCOoCH,

CH ₃

-OCHCO ₂ Ch ₂ CH (CH ₂ ).

according to example

Kp., Mp.,

Bp.: 20 6 ⁰ C 0.07 tnbar

Mp ,: 65-66 ^c C,

[Kp. : 198 ⁰ C ₁

0.01 mbar

Bp.: 190 X ₁ 0.007 mbar

FOKMULIERUNGSBE! GAMES

'Example A

An eraulgierbares concentrate is obtained from

15 parts by weight of "active ingredient

75 parts by weight of cyclohexanone as solvent

and 10 parts by weight of ethoxylated nonylphenol (10AeO) as

Emulsifier.

Example B

A wettable powder easily dispersible in water is obtained by mixing

25 parts by weight of active ingredient

64 parts by weight of kaolin-containing quartz as inert substance 10 parts by weight of lignosulfonic acid potassium

20 and 1 part by weight of oleylmethyltaurine sodium as

Wetting and dispersing agent

mixed and ground in a pin mill.

Ispiel C

A dust is obtained by adding 10 parts by weight of active ingredient

and 90 parts by weight of talc as inert substance

30. mixed and crushed in a hammer mill.

199

Example D

A granulate consists e.g. from about

2 - 15 parts by weight of active ingredient

5 98-85 parts by weight of inert granular material, such as

e.g. Attapulgite, pumice and quartz sand.

 APPLICATION EXAMPLE

Example 1 ·

Various economically important grass weeds and crops were seeded in pots and treated before emergence with the compounds of the invention. The pots were then kept in the greenhouse under good Vachstumsbedingungen. 4 weeks later

1p scored the activity against the grass weeds and the crop selectivity behavior visually for percent damage compared to ^uri treated plants. In this case, the values shown in Table 1, which 'prove that the erfindungsgcmäßon compounds against many weeds are good herbicidal activity and at the same time in high dosages of eg 2.4 kg AS / ha crops or only slightly damage. They are therefore suitable for selective weed control in such cultures.

20.

Example 2

Similarly, the comparison erfindungsgenäßen _2r were sprayed postemergence connections to some important Ungrasarten and various crops, the greenhouse up to the size of 8 - had been attracted 15 cm. Mach further 4 weeks of life im'Gewächshaus the plants were scored visually in terms of their _ ₀ percentage damage by the herbicide treatments. The results, shown in Table 2, show that compounds according to the invention can also be used in the downstream processes for the selective control of weeds in numerous dicotyledonous and monocotyledonous cultures, such as, for example, cotton or rice.

Table 1

Effect and selectivity of the compounds in the pre-emergence process

example kg AS / ha ' AL effectiveness SA Selectivity in culture GS BA * O ) AL ^; . = •. ι Alopecurus · No. against in % plant (injury in $> \ O jSCG = - VO Schinochloa 2.4 100 ECG 100 GH 2 5 SA = I Setaria 0.6 100 95 O O O GH = cotton io 2.4 98 100 95 O 5 4 - GS = Soybean 0.6 95 100 90 O O O O BA = sugar beet CVI 99 4 _ 2.4 85 98 90 O O 2.4 85 75 O 90 O 4 2.4 99 90 95. O O 0.6 98 90 - 1 2.4 100 99 95 O O 0.6 98 95 92 - 5 100 O 95

2.4 100 99 100 0.6 96 99. 99 2.4 96 95 95 0.6 92 90 - HV = barley OS = rice

0 2 1 7 4 0 0 0 1 2 0 2 0 -. O 0 0

Table 2 '

Herbicidal activity and selectivity postemergence (Schädigung.in

Example · kg AS / ha AL. No.

ECG

GH CS BA

HV

OS

Claims (1)

219 199 -21- 9.6.1980 AP C 07 D / 219 199 56 900/12 invention claim 1. A herbicidal composition, characterized by a content of a compound of Ji'ormel I. (D worm R is halogen, CP ₃ , HO ₂ , CIT, HH ₂ , (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) -alkoxy, (C ₁ -C ₄ ) -alkylthio or phenoxy, optionally one to three times by halogen, CF ₃ , (C ₁ -C ₄ ) alkyl, HOp or the group -HH-C (O) -Rp may be substituted; η is 0, 1, 2, 3 or 4, A is 0, S, HH or iMCj-O-alkyl, R _{1 is} H or (C ₁ -C ₄ ) -alkyl, Z is a group of the formula 0 00 0 IX, R _R 11 Ii ti π i ° ^ y ° -C-OR ₃ , -CSR ₄ , -C -HH-R ₅ , -C-IT-H ^, S 0 -CHH ₂ , CH, -CH ₂ OH, -CH ₂ -OCR ₉ or -CH ₂ -O-SO ₂ -R ₁₀ , -22- 9.6.1980 AP C 07 D / 219 199 56 900/12 R _1, H ₁ (C ₁ -C ₁₀ ) -alkyl optionally substituted by 1 to 6 halogen, preferably F, Cl, Br and / or by OH,
(C ₁ -cg) -AIkOXi, (C ₁ -C) - AIkJItMo, (C ₁ -cg) -AIkOXi- (Cp-Cg) -alkoxy, halo (C ₁ ~ _C?) -Alkoxy, I. Ethoxy, (C ₁ -C 4) -alkylamino, di- (C ₁ -C 4) -alkylamino, (C ₁ -C) -alkoxycarbonyl, phenyl, oxiranyl and phenoxy, the latter likewise being substituted by up to two times by halogen or (C .. -C.) -Alkyl
may be substituted ;. (Cp-Cg) -cycloalkyl or halo (C _r -Cg) -alkyl; _(C3 -CG) alkenyl, halo _(C3 -CG) alkenyl or (C _r -CG) cycloalkenyl; (C -.-C -) - alkynyl which may be mono- or disubstituted by (C ₁ -C 4) -alkyl, phenyl, halogen or
(C ₁ -Cp) -alkoxy substituted; Phenyl, optionally. One to three times
(C ₁ -C.) - Alkyl, (Cj-Cj-alkoxy, halogen, NO ₂ or
C3? O is substituted; Furfuryl, tetrahydrofurfuryl
or is a cation equivalent of an organic or inorganic ß _ase; R. (C ₁ -Cg) -alkyl, optionally substituted by ( ^c -iC,) - Alkoxi, halogen or phenyl is substituted, the latter may also be mono- to trisubstituted by (C ₁ -C.) ^A alkyl and halogen;
(C ₃ -Cg) alkenyl or phenyl, which is optionally one to three times by (C ₁ -C) alkyl and / or halogen
is substituted; R _{5 is} H, (C ₁ -Cg) -alkyl, hydroxy (C ₁ -Cg) -alkyl or (C ₅ -C 9 -cycloalkyl, 9 199 -23- 9.6.1980 AP C 07 D / 219 199 56 900/12 Rg is H or CH _3, R _{7 is} H, CH ₃ or C ₂ H ₅ , R _{8 is} H, CH ₃ , C ₂ H ₅ or phenyl, Rg (Cj-Cg) -alkyl which is optionally substituted one to three times by halogen, C ₃ -, C ₅ - or Cg-cycloalkyl, (C - Cg) -alkenyl _t phenyl, (C ₁ -C.) -Alkylphenyl, (Cj-Cj-alkoxiphenyl, halophenyl, trifluoromethylphenyl or nitrophenyl R ₁₀ (C 1 -C 4) -alkyl or phenyl which is optionally monosubstituted to trisubstituted by halogen, CP 1, NO ₂ or (C 1 -C 4) -alkyl, In addition to the usual additional and Pormulierung3hiIfsmitteln.