DD141449A5 - SELECTIVE HERBICIDE MEDIUM - Google Patents

Description

Selective herbicidal agent containing phenylurea derivatives

Applicable Field of the Invention

The invention relates to a selective herbicidal composition containing novel phenylurea derivatives. The novel η herbicidal compositions are used in horticulture and in the agricultural and agricultural sector,

is ^

Phenyl urea derivatives having herbicidal action are already known _s as 1- (3J4 ~ dichlorophenyl) ~ 3S3-diraethyl urea geraäß US P8 2 _e 655 _c ^ 5c These have, however, only a very narrow spectrum of selectivity with respect to crop up, "

The aim of the present invention is to provide a composition which possesses, in addition to an outstanding herbicidal activity against weeds, a broad selectivity spectrum over crop plants. ,

28.5.1979 - 2 - AP A011T / 210 738

Presentation of the Inventory of the Invention;

The invention has for its object to find new phenylurea derivatives find that have excellent herbicidal activity and a broad selectivity spectrum.

This object is achieved by an agent which is characterized in that it contains at least one compound of the general - ^ ormel

/ V

R --VN - CO - NH - U \> OCH - - C - CH

E ₂ R ₃

contains, in the E ^ hydrogen, Cj-C ^ ₂ ^ Alke.nyl, C ₂ -C ^ alkynyl or methoxy, E _{2 is} hydrogen, C ^ -C ^ alkyl, E hydrogen, C ^ -C ^ - Alkyl, E ^ halogen, Ec halogen, X "is hydrogen and / or C ^ -C. alkyl and / or halogen and / or methoxy and η the numbers 1 or 2 _s

The compounds according to the invention are notable for their excellent soil and leaf-herbicidal activity as well as their broad selectivity spectrum over crop plants. They can therefore be used advantageously for combating monocotyledonous and dicotyledonous weeds, in particular in crop plants.

28.5.1979 Ö -3-- 'AP Δ01Ν / 210 738

Arachnids, such as Sinapis spp., Stellaria media, Senecio vulgaris, Matricaria, chamomilla _$ Ipomoea purpurea, Chrysanthemum segetum, Lamium amplexi caule, Centaurea cyanus, Amaranthus retroflexus, Alopecurus myos-uroides are used in the compounds both preemergence and postemergence Echinochloa crus galli, Setaria italica, Loium perenne and other weeds, fought

In order to control seed weeds, application rates of from 1 kg of active ingredient / ha to 5 kg of active ingredient / ha are generally used. The active compounds according to the invention are found to be selective in crop plants, such as bush bean. Peanut, potato, rice, sorghum, corn, winter cereals and soy,

At higher application rates, these compounds are also suitable as total herbicides for the destruction or suppression of a badlands flora during a growing season.

The compounds of the invention may be used either alone, in admixture with each other or with other active ingredients. Optionally, other anti-phagics, pesticides or pesticides may be added according to the desired purpose.

If broadening of the spectrum of action is intended, other herbicides may be added. Examples of suitable herbicidally active compounding agents are active compounds from the group of triazines, aminotriazoles, anilides, diazines, uracils, aliphatic carboxylic acids and halocarboxylic acids, substituted benzoic acids and aryloxycarboxylic acids, hydrazides, amides and nitriles,

28.5.1979 - 4 - 'AB A01N / 210

Esters of such carboxylic acid, carbamic acid and thiocarbamic acid esters, ureas, 2,3,6-trichlorobenzyloxypropanil, rhodan-containing agents and other additives.

Other additives include, for example, non-phytotoxic additives that can give a synergistic effect with herbicides, such as wetting agents, Smalgatoren, solvents and oily additives.

The active compounds according to the invention or mixtures thereof are expediently used in the form of preparations, such as powders, scattering agents, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers or diluents and optionally of wetting, tackifying, emulsifying and / or or dispersing aids applied.

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimetbylsulfoxide, dimethylformamide, furthermore mineral oil fractions.

Suitable solid carriers are mineral earths, for example tonsil, silica gel, talc, kaolin, attaclay, limestone, silicic acid, and vegetable products, for example flours.

Surfactants include for example calcium lignosulfonate _s polyoxyethylene alkylphenol ether, naphthalenesulfonic acids and their salts, phenolsulfonic acids and their salts, pormaldehyde condensates, Pettalkoholsulfato and substituted benzenesulfonic acids and their salts,

28.5.1979 738 - 5 - 'AP A01N / 210 738

The proportion of the active ingredient (s) in the various preparations can vary within wide limits, for example the agents contain about 10 to 80% by weight of active ingredients, about 9 to 20% by weight of liquid or solid carriers and, if appropriate, SU'20 Weight percent surfactants,

The application of the agents can be carried out in a customary manner, for example with water as carrier in spray brewing quantities of about 100 to 1000 liters / ha. Sine application of the funds in the so-called low-volume and ultra-low-volume method is just as possible as their application in the form of so-called microgranules »

As in the general formula for the compounds according to the invention designated radical IL are for example other than hydrogen to understand methyl, ethyl, n-propyl, isopropyl, η-Butylj sec, -Butyl, isobutyl, tert-butyl, allyl, propenyl, propynyl, Butenyl, butinyl, and methpxy and as radicals R ₂ and R "except hydrogen also methyl, ethyl, n-propyl, isopropyl, η-butyl, sec-butyl, isobutyl and tert-butyl,

The radicals R "and Rr- may be fluorine, chlorine or bromine.

The substituent X - may be, for example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, fluorine, chlorine, bromine, iodine, methoxy and others.

Of the compounds of the invention, characterized by an outstanding effect in particular those of the general formula given above, - in the R _{-1 is} methyl or

28.5.1979 - 6 - AP A01H / 210

Metboxy, R _{2 is} hydrogen or methyl, Έ is hydrogen or methyl, H is chlorine or bromine, R _{1 is} - chlorine or bromine, X is hydrogen and / or methyl and / or chlorine and / or Metboxy and η are the numbers 1 or 2.

The new compounds of the invention can be prepared, for example, by

A) compounds of the general formula

C - C - CH

I J

Rp R ^ j

a) with Carbaminsäurehalogeniden the general formula

E - N - CO - Hal ¹ I CH

optionally using a solvent and in the presence of an acid-binding agent or

b) with methyl isocyanate of the formula

CH -N =

05/28/1979.

AP A01N / 21O

if appropriate with the use of a solvent and in the presence of a catalyst or

B) Compounds of the general _formula

Rj . Ες

\ \ / ⁵

O = C = N-

OCH ₀ - C CH

^d IIE ₂ R ₃

with amines of the general formula

NH

CIL

optionally using a solvent and in the presence of a catalyst for the reaction or

C) Compounds of the general formula

/ TV

0 - CO ~ NH

OG hp

mj.t amines of the general formula

R ,. - 1ΤΆ

28.5.1979 - 8 -. AP Δ01Ν / 210

optionally reacted using a solvent or

D) compounds of the general formula

N-CO-CH ₃

with halides of the general formula

^ß 5

Hal CH ₂ -C - CH

I i

H ₂ K

using a solvent and in the presence of an acid-binding agent, optionally in the presence of a catalyst, and the process products isolated in a conventional manner, wherein IL, Rp, EL, '- IL, Ε, -, X and η have the abovementioned meaning and Hai represents a halogen atom.

Suitable solvents in relation to the reactants in all reactions inert aliphatic and aromatic hydrocarbons, such as hexane, benzene and toluene, chlorinated hydrocarbons such as, for example, methylene chloride, chloroform, carbon tetrachloride and

05/28/1979

- 9 -. AP A0W210 738

Dichloroethane, ether, - ie, for example, diethyl ether, tetrahydrofluoroethane and dioxane, ketones, such as acetone and butanone, nitriles, such as acetonitrile, amides, such as dimethylformamide and hexamethylphosphoric triamide.

Suitable acid-binding agents in all reactions are organic bases, such as tertiary amines, for example triethylamine, pyridine and dimethylaniline, or inorganic bases, such as oxides, hydroxides or carbonates of the alkali metal and brominated alkali metals. ,

Suitable catalysts for the Unisetzung with isocyanates

Tertiary amines, such as. Example triethylamine, for the

Reaction of phenols with halides metal iodides, such as sodium iodide «,

The reaction of the reactants takes place in all reactions at temperatures between 0 and 15Ο ⁰ C.

The aniline derivatives to be used as starting materials are obtained by etherification of corresponding nitrophenols and subsequent reduction of the nitro group according to methods known per se.

Conversely, one can first aminophenols regioselectively on, acylate nitrogen and the. Choose an etherification as the last step.

Some of the dibalocyclopropane derivatives to be used for the etherification are already known per se and can be prepared by processes known per se.

28.5.1979 IQ 738 -10- AP A01N / 210

Now, a process has been found which makes it possible to prepare these compounds more easily and in higher yield using inexpensive materials. According to a new method according to the invention an allyl halide of the general formula

- CH = C - CH ₂ Hal

in a two-phase system consisting of a Haloform CHILRt-HaI, optionally diluted by an inert solvent, and an alkali metal hydroxide, solid or as an aqueous solution, in the presence of a catalyst. Surprisingly, the allyl halides used are not or only to a small extent saponified by the alkali metal hydroxides.

Of the haloforms, chloroform and bromoform are preferred, of the hydroxides, the sodium hydroxide, preferably as a 50% aqueous solution.

Suitable catalysts are onium compounds, such as quaternary ammonium, phosphonium and arsonium compounds, and sulfonium compounds.

Also suitable are polyglycol ethers, especially cyclic, such as 18-crown ~6, and tertiary amines, such as tributylamine. Preferred compounds are quaternary ammonium compounds such as benzyltriethylammonium chloride and tetrabutylammonium bromide.

  '28.5.1979

738 - 11 - AP AO12T / 21O

The proportions of the reactants can be varied within wide limits. Preferably, the reactions are carried out with one to ten times the excess of each haloform and of hydroxide. Of the catalyst, 0.02 equivalents are sufficient.

The reaction takes place between 20 and 100 ^° C., but generally between 20 and 60 ^° C. The reaction time is 1 to 72 hours. Throughout the reaction time, good mixing is required.

The Dihalocyclopropanderivate required as Aüsgangsprodukte arise here surprisingly in a higher yield and after a technically simpler procedure ice by known methods.

The following examples illustrate the preparation of the compounds of the invention.

Be i s ρ .i e 1V ,

urea

100 ml (1.16 mol) of 3-bromopropene in 600 ml of chloroform are admixed with 2 g of benzyltriai / hylammonium chloride. Within 30 minutes, 600 ml of 50% sodium hydroxide solution are then added with good stirring. The temperature rises and is maintained by cooling between 56 and 60C. The mixture is stirred for 4 hours at this temperature, then 75O nil chloroform and 750 ml of water are added. The organic phase is separated off, dried, evaporated and fractionated in vacuo. , ,

28.5.1979 - 12 - AP A01N / 210

Yield: 162 g of i-Bro mmethyl ^^ - dichlorocyclopropane Kp ₁₃ : 63-70 ⁰ C, n ^ ° = 1.5096

70 s (0.5 mol) of 4-hitrophenol are dissolved in 250 ml of dimethylformamide and with stirring 108 g (0.53 ¹ o) of 1-bromomethyl-2,2-dichlorocyclopropane, 83 g of potassium carbonate and / 1.5 g of sodium iodide added. The mixture is then stirred at 90 C for 2 hours. Allow to cool, pour on water and extracted with ethyl acetate. The organic phases are washed with dilute sodium hydroxide solution, then with water, dried and evaporated. The residue is crystallized with pentane.

Yield: 113 g of ^ (g- g-dichloro- cyclopropylmethoxy) -

nitrobenzene Melting point: 66 - 67 ⁰ C

108 g (1.73 mol) of hydrazine hydrate are dissolved in 5OO ml of ethanol and 10 g of winding catalyst are added. Within 45 minutes, II3 g (0.43 mol) of the above nitro compound is added in small portions. The temperature rises to 60 ⁰ C. It is allowed to stir for 1 hour, then * filtered, the IPiltrat concentrated and poured into water. It is extracted with ethyl acetate, dried and evaporated. There remains a yellowish oil, which is further reacted without purification.

Yield: 96 g - 4- (2 _r 2 ~ D_i ^ ·

20 g (0.086 mol) of 4- (2,2-dichlorocyclopropylmethoxy) -aniline are dissolved in 100 ml of pyridine. 8.7 ml of dimethylcarbamoyl chloride are added with stirring within 5 minutes.

28.5.1979 - 13 - AP A01N / 210 738

drips, while the temperature 'rises to 53 ⁰ C. The mixture is stirred for 2 hours and then evaporated at 50 torr, largely einβ 'The residue is taken up in silica, washed once with water, once with "5% hydrochloric acid, dried, evaporated and crystallized from isopropyl ether.

Yield: 16 g - 1- £ 4- (2,2-DiC hiOr Cy ^

Melting point: 108-110 ⁰ O.

B e ^ i S ... Jp 1 el 2

barn stof f '

17 S (0.094 mol) of 1,1-dimethyl-3 - (3-hydroxyphenyl) urea, dissolved in 60 ml of dimethylformamide, with 22 g (0.108 mol) of 1 ~ bromomethyl-2j2 ~ dichlorcyclopropari, 16 g of potassium carbonate and 2 g of sodium iodide and stirred at room temperature is added After 20 hours further 6 g of 1-Brommethy1 ~ 2,2-dichlorocyclopropane and 5 g of potassium carbonate are added and allowed to stir for a further 6 hours _t is then strongly concentrated, taken up in _Essigester? extracted with water, dried and crystallized from There sigester / ether,

Yield: 19.9 S Melting point: 140 - 142 ⁰ G

The 1 used as a starting material Au _{S S} 1-Dirnethyl-3- (3 ~ hydroxyphenyl) urea is known per se and can be prepared, for example from 3-aminophenol and dimethylcarbamoyl chloride by methods known per se "-

28.5.1979 - 14. - AP Δ01Ν / 210

In an analogous manner, the following compounds according to the invention can be prepared.

Name of the connection Physical

constant

1-F4- (2,2-Dichlorcyclopropylmethoxy) - mp: 163 ~ 164 ⁰ C.

3-methoxyphenyl] -3,3'-dimebbylharn

material . -.

1-F4- (2,2-Dichlorcyclopropylmethoxy) ~ Pp: 105-106 ⁰ C.

3-methoxyphenyl3-3 metho: ^ - 3-methyl

urea

1-.D ~ ^ch lor-4- (2.2-dicblorcyclopropyl ~ Pp: I30 - I31 C ⁰

methoxy) -phenylj-3,3-dimethyl thiourea

1- £ 3_Chlor-4 ~ (2,2-dichlorocyclopropyl-Pp: 79-80 ⁰ G

met hoxy) -phenyl] -3-tnethoxy-3-methylurea "'·

1- £ 4- (2,2-Dichlorcyclopropylniethoxy) ~ Pp: 88-89 ⁰ C

phenyl] -3-methoxy-3-methyl-urea

1-Butyl-3-C4- (2,2-dichlorocyclopropyl-Pp: 87-88 ⁰ C)

methoxy) ~ phenylj-1-methylurea

1-f 4 - (2,2-Dictibryclopropylmethoxy) - Pp: 111 - 113 ⁰ C

phenylT-3-methyl-3- (1 ~ methyl-2-

propynyl) urea

i - ^ - ^^ - Dichlorcyclopropylmethoxy) - Pp: 135 - 136 ⁰ C.

3,5-dimethylphenyl] -3,3-dimethylurea

1-r4- (2,2-dicyclopropylmethoxy) ~ Pp: 66- 67 ⁰ G

5dithlblj ^ th ^ thl

, y 3,5 ~ dimethylphenyl} - barium

1 - /] 4- (2 ₎ 2-dichlorocyclopropyl-niethoxy) - Pp: 146 - 147 ° C

1-r4- (2,2-dichlorocyclopropylmethoxy) - Pp: 111 - II3 ⁰ C

3-methylphenyrj-3,3-di-ethylurea.

1-butyl-3-D- (2-2 dichlorcyclopropyl- _Pp: 71-72 ⁰ C

methoxy) phenyl] -1 ~ methyl-urea

28.5.1979 AP.A01N / 210 738

Name of Verbinauni

Physical constant

1-Γ4-42,2-dichloro-1-trimethyl-cyclopropyl-Fp: IO3 -104-G

me'thozy; -phenyl] -3-methcocy-3-methyl

urea

1-p- (2,2 ~ dichloro-1-methylcyclopropylme-choxy) -phenylJ-3,3-ainiethylharnstofx

1-I-1- (2-yl-dichloro-1-methyl-cyclopropyl-methoxy) -phenyl] -3 _s 3- ^< 3-i-diethylurea

1- C3 ~ (2,2 ~ Mbromcyclopropylm.ethoxy) -phenyl] -3,3-dimethylurea

1 - 4 - (2 j 2-dibromo-cyclopr opylmethoxy) phenyl] -3,3-dimethybutylurea

1 - [A- (2 _v 2-dichloro-3-methylcyclopropylmethoxy) -phenyl] -3,3-dimethyl-halo-1-r 3 - (2 ₅ 2-dichloro-3-methylcyclopropylmethoxy) -phenyl.] - 3 _s 3-dime thyl urea

Mp: 105 - 106 ⁰ C ρ: · 127 - 128 ^U C

Mp: 112-113 ^U C mp: 99-101 ⁰ C: 140-142 ° C

Mp: 102-104 ⁰ C

The phenylurea derivatives according to the invention are colorless and odorless, crystalline substances which are readily soluble in ethyl acetate, acetone and alcohol, some of which dissolve only moderately in benzene and are practically insoluble in saturated hydrocarbons and water.

The following examples serve to illustrate the applications and the superior selective herbicidal activity of the compounds of the invention.

Example 3

In the greenhouse, the compounds according to the invention listed in the table were _s in an application rate of

, 28.5.1979 - 16 - 'AP Δ01Ν / 210

5 kg of active ingredient, in 500 liters of water / ha as aqueous emulsions on Sinapis sp. and Solanum sp. injected as test plants in the pre- and post-emergence. 3 hours after the treatment, the treatment result was rated, with.

0 = no effect and

4- = destruction of the plants

mean. As can be seen from the table, destruction of the test plants was generally achieved.

05/28/1979

AP A 0111/210 738

Pre-emergence Sinapis sp.

Compounds of the invention Solanum sp.

Ha c ha lauf Sinapis sp.

Solanum sp,

i-G ^ - ^^ - Dichlorocyclopropyl-4,4-methoxy; -3-methoxyphenyl] -3,3-dimethylurea

1-r4- (2,2-dichlorocyclopropyl-4,4-methoxy) -3-metboxyphenyl] -3-methoxy-3-methylurea

1- / 3-Chloro-4- (2,2-dichlorocyclo-4,4-propylmethoxy) -phenylJ-3j3-di-metbylurea

1_ ^ 3_, chloro «4 ~ (2,2-dichlorocyclo-4,4-propylmethoxy) -phenylj-3-methoxy ~ 3-methylurea

1~4- (2,2-dichlorocyclopropyl-4,4-methoxy; -phenyl-3-methoxy-3 ™ methylurea

1-butyl ~ 3 ~ £ 4- (2j-2-dichlorocyclo - 4 4

propylmethoxy) -phenylj-1-inethylharnstoff

1-r4- (2,2-dichlorocyclopropyl-4,4-methoxy; -phenyl) -3-ethyl-3- (1-hydroxyethyl) -propyl) urea

4 4

^ (, YPPy

methoxy) -phenylj ~ 3,3-dimethyl ~ urea

1 "jf4 .-. (2 _> 2-D: lchlorocyclopropylmethoxy) -3j5-dimetbylphenylyl-353-dimethylurea

'l-f4- (2,2-dichloro-cyclopropyl-methoxy; -3 _s 5-dimethyl-phenyl) -3-methoxy-3-methyl-urea

1-i.4- (2.2 Dichlorcyclopropyl-

methoxy) -3 ~ ra.3thylphenyl] ~ 3J3-dimethylurea

1 ~ r4- (2,2-dichlorocyclopropyl ~

methoxy; 3, 5-dichlorophenyI-i-3j3-dimethylurea

05/28/1979

AP A01H / 210 73 ⁸

  , preemergence

Sirgapis sp.

Compounds of the invention 'Solarium sp.

Snack casserole Sinapis sp.

Solan at sp.

^ yppy

-methoxy-phenyIJ-3, -3-dimethiourea.

1-r4- (2,2-dichloro-1-iiietbylcyclopropylmethoxy) -phenyl] -3-methoxy- "3-niethylharnstoff

1-f3 ~ (2,2-dibromocyclopropylmethylthoxy) ~ phenyl.j ~ 3,3-dimethylbenzyl

1-D- (2,2-dichloro-1-methylcyelopropylmethoxy) -phenyl] -3,3-di-ethyl-urethane

1-Butyl-3-i3- (2,2-dcyclopropylmethoxy) -phenyl 3j, 1-methylurea

1- & f- (2,2-dichloro-1-niethylcyclopropyl-line-thoxy) -phenyl] 3j3-dimethylurea

1-r3- (2j-dichloro-cyclopropyl-methoxy) -phenyl] -3 ₁ 3-dimethyl-urea

1- (4- (2 ₅ 2-dichloro-3-methyl)

cyclopropylmethoxy) phenyl) -3 _i 3-dimethylurea

1- (3 -. (2,2-dichloro-3-methyl-

cyclopr ofiyl-me thoxy) -phenyl) - "3j3-dimethylurea

, 4

28.5.1979 - 19 - "AP Δ01Ν / 210

B ^ e _- i, S ₁ ρ ie 1 4 ·

In the greenhouse, the plants listed in the following table after emergence were treated with the agents according to the invention at an application rate of 1 kg of active ingredient / ha. The compositions were sprayed uniformly over the plants in the form of aqueous emulsions for this purpose. Also beer showed 3 weeks after the treatment.

 the agents according to the invention have a high compatibility with crops with excellent activity against the weeds. The comparison agent did not show this selectivity. The treatment result was scored, with

O = totally annihilated and 10 = not damaged

mean*

* J

-

O vj _Λ η cd it * d -λ VJJ-λ he I Hi O "β I CD H he! I ι CD H) Il vj £ 3 0 *} σ * £ 3 p- it -K H- Il I vj P- H it 5? CD - |> VJ I it et P ¹ Co CD CD et i .H C5 O H- H- I * y * "* \ CT / -N ro H- Cf P ; go he Year rv) I O CO CD Ö I ** H- vj ro CTQ he H ct H- I CQ VJJ ro * Ö ΓΟ I CQ ct CT O I i he ι vj tJ era <i vj he iJJH · D B fc> CD Hj I H- CD m CD H I- ' ct CD H it η · O CD H. he O ROCT pj ci- O Vj o H- he CQ CO • φ he he He H · CD O H- H, (Ti H CD O H l_J | 1 CD O CT O CS he vji M O ι ο ct H p: he CQ CD * sJ1 H Year H ₁ VjJ H, CT O CD P · ct ct XS • I o - O V { H H- CD O Vl tt VjJ «j H O O" era ct H) H Ό1 JO 1 o he H ind ct Η " v ' Ö ι ι ΡΉ co O P I CD O H-O it H it CTH CD f-J CQ O CD Vj o CTO et XS H ^ he <x} Η) H CB H H) H. 0 CD CS ω about CD ct co ci- H et he he it tr ο - ο o CQ O

vj

ch u>

ro

VJI

O O

O O

O O O O

Η> "<ί

 ι

O O O

H) J

O O

I O

O O O O

O O

O I

O O O O

Barley wheat.

Corn

Rice carrots

Alopecurus myosaroides

Galiam aparine

Ma tricaria chamomilla

Chrysanthemam segetam

Polygonum lapathifoliam

Claims (2)

28.5.1979 - 21 - AP AOiN / 210 738 R esp o ration 1, Selective herbicidal agent, characterized in that it Phanylharnstoff derivatives of the general. ^ N-CO-OT-U -ßr- OCH ₀ - C 'CH CH ₃ R ₂ R ₃ contains in which R ^ is hydrogen, C.-C.-alkyl, C ₂ -C.-alkenyl, C ₂ ~ C-alkynyl, or methoxy, R ₂ is hydrogen or C ^ jC ^ alkyl, R 'is hydrogen or C ^ - C. alkyl, R is halogen, R ₁ - halogen, X is hydrogen and / or C ^ -C.-alkyl and / or halogen and / or methoxy, and η is the number 1 od.er 2 ^ mean, in admixture with carrier and / or auxiliaries. 2, Selective herbicidal composition according to item 1 _}, characterized in that R ^ is methyl or methoxy, Rp is hydrogen or methyl, R-, hydrogen or methyl, R ^ is chlorine or bromine, X is hydrogen and / or methyl and / or chlorine and / or .-. Methoxy and η are the numbers 1 or 2.