DD249622A5 - HERBICIDE MEDIUM - Google Patents

Abstract

Strong herbicidal activity, good crop tolerance, selective weed control in crops, regulation of plant growth. The invention relates to herbicidal compositions containing new tetrahydroisoindolinones of the formula I in which R 1 is alkyl, R 2 -phenyl, naphthyl, pyridyl, quinolinyl or isoquinolinyl which may be substituted, a radical of the formula C (O) XR 3, OP (Z) (YR 4 ) 2 or Z (CHR5) 2COXR3, A is a radical of the formulas. or NNCS and m0, 1 or 2. The compositions according to the invention have advantageous herbicidal properties compared to mono- and dicortylen Schadpflanzen. formulas

Description

is substituted,

wherein X, Z = O or S, R ³ = (C ₁ -C ₆ ) AlkYl, (Ci-C ^ alkoxycarbonyl-FC ^ CJalkyl or

(Cv-C ₄₎ alkoxy (Ci-C4) alkyl; R ⁵ = H or (C ₁ -C ₂ ) Alkyl- A = a radical of the formula -P (O) R ⁹ R ¹⁰ , where

R ⁹ , R ¹⁰ = independently of one another (C ₁ -C ₄ ) mean AIkYl, phenyl, OH or OM, and m is O.

stands mean.

4. Use of the compounds of formula I of claims 1, 2 or 3, characterized in that they are used as herbicides.

5. A method for controlling undesirable plants in crops, characterized in that applying to the harmful plants or the acreage an effective amount of a compound of formula I of claims 1, 2 or 3.

Field of application of the invention

The invention relates to new herbicidal compositions containing new tetrahydroisoindolinones.

The compositions according to the invention are used in agriculture for the selective control of weeds in crops as well as for the growth regulation of crop plants.

Characteristic of the known technical solutions

It is known that certain tetrahydroisoindolinone derivatives have herbicidal properties, s.z. For example, EP-A 40849, EP-A 41256.

Object of the invention

The aim of the invention is the provision of new agents with a strong herbicidal action, a broad spectrum of activity and good "" compatibility with crops, which are suitable for selective weed control in crops.

Explanation of the essence of the invention

The object of the invention is to find new round compounds having the desired properties which are suitable as active ingredient in the novel herbicidal compositions. There have now been found new Tetrahydroisoindoline with beneficial herbicidal effects.

According to the invention as the active ingredient in the novel herbicidal agents new 4,5,6,7-tetrahydroisoindolinones of the general formula I.

(I)

applied, in which

R ¹ = (C ₁ -C ₄ ) Alkyl;

R ² = phenyl, naphthyl, pyridyl. Quinolinyl or isoquinolinyl, where these radicals are one to four times,

preferably one to three times, by identical or different radicals of the group halogen, hydroxy, (C ₁ -C ₄ ) AlkYl, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) alkoxy, (C ₃ -C ₆ ) CyCl oc I koxy, (C ₃ -C ₆ ) alkynyloxy, (C ₁ -C ₆ -alkynyloxy, halogeno (C ₁ -C ₄ -alkyl), halogen (C ₁ -C ₄ ) alkoxy, halo (C ₃ -C ₆₎ alkenyioxy, halo (C ₃ -C ₆ JaIWnYiOXy, (dC ₄₎ alkylthio, (C ₁ -C ₄₎ AIkylsulfinyl, (dC ₄₎ alkylsulfonyl, wherein the at the three last-mentioned radicals alkyl radical by (C ₁ -C ₄₎ alkoxycarbonyl may be substituted, NO _2, CN, C ^ alkyl-Halogenld, cyano (C ₁ -C ₄₎ alkyl, phenoxy, phenoxy (Ci-C ₄₎ alkyl, PhenyKd- C 1-6 -alkoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, where the six last-mentioned radicals in the phenyl ring are up to three times halogen,

(C ₁ -C ₄ ) Alkyl, (C ₁ -C ₄ ) alkoxy or (C ₁ -C ₄ ) alkoxyCaTbOnYl may be substituted, or by a radical of the formulas'. -._.!

"""z R ⁵ O

-3 " a I Il,

-CXR ³ , -OP (YR ⁴ ) ₂ or -Z- (CH) _n -CXR ³

can be substituted

X = O, S or NR ⁶ ,

Y ₁ Z = independently of _one anotherO or S,

R ³ = hydrogen, (C ₁ -C ₁₂ ) alkyl radical which is up to 6-fold halogen and / or up to twice (C ₁ -C ₄ ) -alkoxy,

(C ₁ -C ₄₎ Arkoxy (C ₁ -C ₄₎ alkoxy, (dC ₄ alkoxy) carbonyl, (C ₁ -C ₄₎ AIkYHhIO, (dC ₄₎ alkylsulfinyl, (d-CJAIkylsulfonyl, (C ₁ - C ₄ ) alkylamino, di (C ₁ -C ₄ ) alkylamino, furyl, tetrahydrofuryl, benzofuryl, phenyl, phenoxy, benzoloxy, wherein the phenyl rings are up to three times halogen, (C ₁ -C ₄ alkyl or (C ₁ -C ₄ ) AIkOXy may be substituted,

(C ₃ -C ₆₎ cycloalkyl, _(C3-C6) alkenyl, cyclohexenyl, _(C3-C6) alkynyl, phenyl which may be substituted up to three times by halogen, (C ₁ -C ₄₎ -alkyl, (C ₁ -C ₄ ) AIkOXy or (d-CiAlkoxyl-carbonyl; a radical of the formula

-N = C

or a cation usable in agriculture; R ⁴ = (C ₁ -C ₄ ) alkyl,

R ⁵ = hydrogen, (C ₁ -C ₄ ) alkyl,

R ⁶ = hydrogen, (C ₁ -C ₄ ) alkyl, which, together with R ³ and the nitrogen atom connecting these radicals, has a five-bis

can form a seven-membered heterocycle containing as ring members one or two radicals of the group -O-, -S-, NR ⁵ and can be substituted up to three times by (C ₁ -C ₄ ) alkyl,

R ⁷ , R ⁸ = independently (dC ₄ ) alkyl, (C ₃ -C ₆ ) cycloalkyl or together a (C ₂ -C ₇ ) alkylene chain; A = a remainder of the formulas

I! 9 -P-R or -NCS,

k ¹⁰

R ⁹ , R ^{10 are} independently (C ₁ -C ₄ ) alkyl, phenyl or benzyl, both of which are up to two times halogen, (C ₁ -C ₄ ) alkyl,

CF ₃ or (C ₁ -C ₄ ) alkoxy may be substituted; (C ₁ -C ₄ ) alkoxy; (C 1 -C ₄ ) -alkylthio; OH, SH, OM or SM, where M is an agriculturally usable cation, or a radical of the formula -NR ¹¹ R ¹² ,

R ", R ¹² independently of one another are hydrogen; (C ₁ -C ₆ ) Al-alkyl; phenyl or benzyl, both of which are up to two times halogen,

(C ₁ -C ₄ ) Alkyl, CF ₃ or NO ₂ may be substituted, the R ¹¹ and R ¹² together with the adjacent N-atom

a five- to six-membered heterocycle containing as ring members one or two radicals of the group -O-, -S- or -NR ⁵ -

and which may be substituted up to three times by (C 1 -C ₄ ) alkyl; m = 0,1 or 2 and

η = 1,2 or 3

mean.

The rest halogen (Ci-C ₄ ) alkyl contains in particular one to three fluorine, chlorine or bromine atoms. Halogen (C ₁ -C ₄ ) -alkoxy contains more than one to nine fluorine, chlorine or bromine atoms, halogen (C ₃ -C ₆ ) alkenyloxy, preferably one to seven fluorine, chlorine or bromine atoms and halo (C ₃ -C ₆ ) alkenyloxy one to five fluorine, chlorine or bromine atoms.

The compounds of the formula I can be present as pure stereoisomers or mixtures thereof, depending on the radicals (for example in the case R ² = -Z-CH (R ⁵ JCO-XR ³ and R ⁵ ΦΗ) Preferred compounds of the formula I are those compounds in which R ² = phenyl, pyridyl, both of which may be substituted once to three times by (C ₁ -C ₄ ) alkyl, which may be substituted by up to three times by halogen,

by F, Cl, Br, (C ₁ -C ₄ ) -alkoxy, which may be up to nine times substituted by fluorine and / or chlorine, by (dC ₄ ) alkylthio, -CO-XR ³ or

-Z- (CH) _n -CO-XR ⁵ JT - -

are substituted, X, Y, Z = O or S,

R ³ = (d-CeiAlkyUd-C ^ alkoxycarbonyl-id-Ctialkyloderfd-C ^ Alkoxy-fC ^ C ^ alkyl,

A = a remainder of the formulas

R ⁹ , R ¹⁰ = independently of each other (C ₁ -C ₄ ) AlkYl; Phenyl or benzyl, both of which up to two times by halogen, (Ci-C ₄₎ AIkyI, CF ₃ or (C ₁ -C ₄₎ -alkoxy may be substituted; (C ₁ -C ₄ ) alkoxy; (C 1 -C ₄ ) -alkylthio; OH, SH, OM or SM, where M is an agriculturally useful cation, or a radical of the formula -NR ¹¹ R ¹² and

R ¹¹ , R ¹² = independently of one another hydrogen; (C ₁ -C ₆ -alkyl) phenyl or benzyl, both of which may be substituted by up to three times by halogen, (C ₁ -C ₄ ) alkyl, CF ₃ or NO ₂ or R ¹¹ and R ¹² together with the adjacent N Atom is a five- to six-membered heterocycle which may contain as ring members one or two radicals of the group -O-, -S- or -NR ⁵ - and which may be substituted by (Ci-C ₄ ) AlkyI up to three times;

η = 1,

m = O or 1.

Particularly preferred compounds of the formula I are those compounds in which

R ² = phenyl, which is 1 to 3 times by (C ₁ -C ₄ ) AlkYl, which may be substituted by up to three times by halogen, F, Cl, Br,

(C ₁ -C ₄ ) alkoxy, which may be substituted up to three times by fluorine and / or chlorine, (dC ₄ ) alkylthio, -CO-XR ³ or

-Z-CH-CO-X-R ^.

is substituted,

wherein X, Z = O or S, R ³ = (C ₁ -C ₆ ) AlKyl, (d-dJ-alkoxycarbonyl-iCi-CJalkyl or (dC ₄ ) alkoxy- (dC ₄ ) alkyl;

R ⁵ = H or (C ¹ -C ₂ ) alkyl, A = a radical of the formula -P (O) R ⁸ R ¹⁰ , where

R ⁹ , R ¹⁰ = independently of one another (C 1 -C ₄ ) alkyl, phenyl, OH or OM, and m is O. Suitable heterocycles for the radical R ³ -NR ⁶ are preferably morpholine, piperidine, piperazine, pyrrolidine. Another object of the application is a process for the preparation of the compound of general formula I, characterized in that a compound of formula II

^Λ (II),

wherein R ^{12 is} a nucleofugic group such as halogen, tosyl or mesyl, with a compound of formula H-A ',

M-SCN or, 9

R-10

RY-P, where A 'is the meaning of A except

^ r9 -P (Y). and SCN- and M has a metal cation,

preferably a lead (II), potassium or Na ion, is reacted, and the compounds obtained, if desired, derivatized.

The reaction of the compound of formula II with the compound H-A 'is preferably carried out in the presence of an inorganic base such as. Example, potassium carbonate, sodium hydroxide or sodium hydride or an organic ', preferably a tertiary nitrogen base, such as triethylamine or pyridine in an inert organic solvent such as acetonitrile or dimethylformamide at temperatures between 40 and 160 ° C, preferably between 60 and 100 ° C.

The reaction of II with a phosphorous acid triester, phosphonous diester or phosphonous acid monoester of the formula Ff-Y-PR ⁹ R ¹⁰ is preferably carried out without solvent at temperatures between 50 and 140 ^G C, optionally under potassium iodide catalysis. If desired, the phosphonic or phosphinic esters obtained in this case can be converted into the phosphonic acid or phosphinic acid by customary methods. These in turn can be converted by conventional methods into the corresponding salts, phosphonic or phosphinamides. The reaction of II with a rhodanide of the formula M-SCN is carried out in an inert organic solvent such as toluene, acetone or dimethylformamide at temperatures between 0 and 100 ° C, preferably at 50-80 ° C.

The tetrahydroisoindolinones of the formula II are partially known in the case of II ¹² = Cl according to DE-OS 2831 770, EP-A-40849 / Other compounds of the formula II can be prepared in a simple manner from the 3-hydroxy-4,5,6,7 Tetrahydroisoindolinonen of the formula III with a halogenating agent, such as thionyl chloride in the usual way (see German Patent Application P 3533442.8.).

, 0H

The compounds of formula III are also known (DE-OS 2831 770) or can be prepared in a simple manner from the 3,4,5,6-tetrahydrophthalimides of the formula IV with a reducing agent such as NaBH ₄ , in a known manner, (s. Rocz. Chem., 49, 1671 (1975).

uv)

In turn, the compounds of the formula IV can be prepared from 3,4,5,6-tetrahydrophthalic anhydrides and the corresponding amines by customary methods.

The compounds of the formula I according to the invention have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. Even difficult to control perennial weeds, which expel from rhizomes, rhizomes or other permanent organs, are well detected by the active ingredients. It does not matter whether the substances are applied in pre-sowing, pre-emergence or post-emergence procedures.

For example, the following harmful plants can be controlled:. _ _

Weed grasses like Avena fatua, Alopecurussp

 Lolium sp

 Setaria sp

 Digitaria sp

 Sorghum halepense Echinochloa sp

 Agropyronsp

 Cynodon sp

 Phalarissp., Dicotyledonous plants such as Lamium sp

 Veronica sp

 Galium sp.

Stellaria sp.

Matricaria sp.

Papaversp.

Centauria sp.

Amaranthus sp.

Galinsogasp.

Mercurialis sp.

Sida sp.

Abutilon sp.

Ambrosia sp.

Xanthium sp.

Cirsiumsp.

Artemisia sp.

Rumexsp.

Convolvulus sp.

Ipomeasp. '

Sinapissp.

If the compounds according to the invention are applied to the surface of the earth before germination, either the emergence of the weed seedlings is completely prevented, or the weeds grow to the cotyledon stage, but then cease their growth and finally die completely after three to five weeks.

Upon application of the active ingredients to the green plant parts in the postemergence behavior, a drastic growth arrest also occurs very rapidly after the treatment, and the weed plants remain in the growth stage existing at the time of application or die off more or less rapidly after a certain time, so that these A harmful to the crops weed competition can be eliminated very early and sustainable by the use of the novel agents of the invention.

Although the compounds of the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crops of economically important crops such as e.g. As wheat, barley, rye, rice, corn, sugar beet, cotton and soy only insignificant or not damaged. For these reasons, the present compounds are very well suited for the selective control of undesired plant growth in agricultural crops.

In addition, the compounds according to the invention have growth-regulating properties in crop plants.

They regulate into the plant's metabolism and can thus be used to facilitate harvesting such as. B. by triggering desiccation, abscission and stunted growth. Furthermore, they are also suitable for the general control and inhibition of undesirable vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous cultures, as storage can be reduced or completely prevented.

The compositions according to the invention can be used as wettable powders, emulsifiable concentrates, sprayable solutions, dusts, mordants, dispersions, granules or microgranules in the customary formulations.

Injectable powders are preparations which are uniformly dispersible in water and, in addition to the active substance, may also contain wetting agents, for example a diluent or inert substance. As polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenylsulfonates and dispersants, eg. As sodium lignosulfonate, 2,2'-dinaphtylmethane-6,6'-disulfonic acid sodium, dibutylnaphthalenesulfonate sodium or oleoylmethyltaurine acid. The preparation is carried out in a conventional manner, for. B. by grinding and mixing of the components.

Emulsifiable concentrates may e.g. by dissolving the active ingredient in an inert organic solvent, e.g.

Butanol, cyclohexanone, dimethylformamide xylene or higher-boiling aromatics or hydrocarbons are prepared with the addition of one or more emulsifiers. In the case of liquid active substances, the proportion of solvent can also be omitted completely or partially. Examples of emulsifiers which may be used are: alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide / ethylene oxide condensation products, fatty alcohol / propylene oxide / ethylene oxide condensation products, alkylpolyglycol ethers, sorbitan fatty acid esters, polyoxethylenesorbitol esters.

Dusts can be obtained by grinding the active substance with finely divided, solid substances z. Talc, natural clays such as kaolin, bentonite, pyrophillite or diatomaceous earth.

Granules can be prepared either by spraying the active ingredient on adsorptive, granulated inert material or by applying active substance concentrations by means of binders, for. As polyvinyl alcohol, poyacrylsaurem sodium or mineral oils on the surface of carriers such as sand, kaolinites or granulated inert material.

Also, suitable active ingredients may be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.

In wettable powders, the drug concentration is e.g. about 10 to 90% by weight, the remainder to 100% by weight consists of customary formulation constituents. For emulsifiable concentrates, the concentration of active ingredient may be about 5 to 80% by weight.

Dusty formulations usually contain 5 to 20 wt .-% of active ingredient, sprayable solutions about 2 to 20 wt .-%.

For granules, the active ingredient content depends in part on whether the active compound is liquid or solid and which granulation aids, fillers, etc. are used.

In addition, the active substance formulations mentioned optionally contain the usual adhesion, wetting, dispersing, emulsifying, penetrating, solvent, filling or carrier substances.

For use, the concentrates present in commercial form are optionally diluted in conventional, e.g.

for wettable powders, emulsifiable concentrates, dispersions and sometimes also for microgranules by means of water.

Dusty and granulated preparations as well as sprayable solutions are usually no longer diluted with other inert substances before use.

With the external conditions such as temperature, humidity and the like. the required application rate varies. She can be inside

continue to fluctuate borders, z. Between 0.005 and 10.0 kg / ha or more of active substance, but is preferably between 0.01 and 2 kg / ha.

Also mixtures or mixed formulations with other active ingredients, such as. As insecticides, acaricides, herbicides, fertilizers, growth regulators or fungicides may be possible.

embodiment

The invention is illustrated by the following examples.

A. Formulation Examples

A dust is obtained by mixing 10 parts by weight of active compound and 90 parts by weight of talc or inert substance and comminuting in a hammer mill.

A wettable powder readily dispersible in water is obtained by mixing 25 parts by weight of active ingredient, 64 parts by weight of kaolin-containing quartz as an inert, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurate as a wetting and dispersing agent and grinding in a pin mill.

A dispersion concentrate readily dispersible in water is obtained by reacting 20 parts by weight of active compound with 6 parts by weight of alkylphenol polyglycol ether (®Triton X207), 3 parts by weight of isotridecanol polyglycol ether (8AeO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to more than 377 ° C.). mixed and ground in a ball mill to a fineness of less than 5 microns.

An emulsifiable concentrate is obtained from 15 parts by weight of active compound, 75 parts by weight of cyclohexynone as solvent and 10 parts by weight of ethoxylated nonylphenol (10AeO) as emulsifier.

B. Chemical Examples

Example 1 2- (4-Chloro-2-fluoro-5-methoxy-phenyl) -3-imidazol-1-yl-4,5,6,7-tetrahydroisoindolinone 1.36g (20.0 mmol) imidazole and 2, 76 g (20.0 mmol) of potassium carbonate are heated to 60 ° C. in 40 ml of acetonitrile. At 60 ° C is added dropwise 6.40 g (20.0 mmol) of 3-chloro-2- (4-chloro-2-fluoro-5-methoxyphenyl) -4,5,6,7-tetrahydroisoindolinone, dissolved in 20 ml of acetonitrile , too. The mixture is stirred for 4 h at 60-7O ⁰ C until the reaction beewdet is.-The mixture is poured onto 250 ml of water and extracted with 100 ml of methylene chloride. The methylene chloride phase is washed again with 100 ml of water and dried over sodium sulfate. After distilling off the solvent, the remaining solid residue is triturated with petroleum ether and filtered with suction. This gives 5.6 g (80.0% of theory) of 2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-imidazol-1-yl-4,5,6,7-tetrahydroisoindolinone in the form of tan crystals with m.p. 78-85 ° C.

Example 2 2- [4-Chlorophenyl] -3- (1,2,4-triazol-1-yl) -4,5,6,7-tetrahydroisoindolinone

1.38 g (20.0 mmol) of triazole and 2.76 g (20.0 mmol) of potassium carbonate are heated to 60 ° C. in 40 ml of acetonitrile. At 6O ⁰ C is added dropwise · 5,64g (20,0mmol) of 3-chloro-2- (4-chlorophenyl) -4,5,6,7-tetrahydroisoindolinon dissolved in 20 ml of acetonitrile to. The mixture is stirred at 70 ° C until the reaction is complete (5 h) and poured into 250 ml of water. It is extracted with 100 ml of methylene chloride, the methylene chloride phase is washed with 100 ml of water and dried over sodium sulfate. After distilling off the solvent, the remaining solid residue is triturated with petroleum ether and filtered with suction. This gives 5.40 g (86% of theory) of 2- (4-chlorophenyl) -3- (1,2,4-triazol-1-yl) -4,5,6,7-tetrahydroisoindolinone in the form of pale yellow crystals with mp. 64-68 ⁰ C.

Example 3, 2- (4-Chloro-2-fluoro-5-isopropoxyphenyl) -3-diethoxyphosphoryl-4,5,6,7-tetrahydroisoindolinone 17.9 g (0.05 mol) of 3-chloro-2- (4 chloro-2-fluoro-5-isopropoxy-phenyl) -4,5,6,7-tetrahydroisoindolinon and 10.0 g (0.06 mol) of triethyl phosphite are heated at 70 ⁰ C with 30 mg potassium iodide. After completion of the gas evolution is heated to 100 ⁰ C for 30 min. The partially kristaliierende during cooling reaction mixture is heated with 150 ml of ether and the precipitate sucked off. This gives 21.2 g (92% of theory) of 2- (4-chloro-2-fluoro-5-isopropoxyphenyl) -3-diethylphosphoryl-4,5,6,7-tetrahydroisoindolinone in the form of colorless crystals with mp 108-110 ⁰ C.

Example 4 2- (4-Chloro-2-fluoro-5-methoxy-phenyl) -3-rhodano-4,5,6,7-tetrahydroisoindolinone 6.4g (0.02mol) 3-chloro-2- (4- chloro-2-fluoro-5-methoxy-phenyl) -4,5,6,7-tetrahydroisoindolinon and 3.2 g (0.01 moi) BleidDrhodanid be in 80 ml of toluene for 3 hours at 7O ⁰ C heated. It sucks from the formed lead chloride, the ToIu oil phase washes briefly with 100 ml of water, dried over sodium sulfate and the solvent is distilled off. The residue is dried at 4O ⁰ C under vacuum to constant weight. This gives 6.3 g (92% of theory) of 2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-rhodano-4,5,6,7-tetrahydroisoindolinone in the form of a viscous yellow oil ,

Example 2- (2-Chloro-4-fluoro-5-methoxy-phenyl) -3-pyrrolyl-4,5,6,7-tetrahydroisoindolinone Dissolve 1.34 g (0.02 mol) of pyrrole and 2.0 g (0, 02mol) triethylamine in 40 ml of toluene and added dropwise at RT6.4g (0.02 mol) of 3-chloro-2- (4-chloro-2-fluoro-5-methoxyphenyl) -4,5,6,7-tetrahydroisoindolinone dissolved in 30 ml of toluene, too. The mixture is stirred for 3 h at 7O ⁰ C, washed twice with 100 ml of water and dried over sodium sulfate. After removal of the solvent, 6.20 g (89% of theory) of 2- (2-chloro-4-fluoro-5-methoxyphenyl) -3-pyrrolo-4,5,6,7-tetrahydroisoindolinone in Form of a brown oil. In an analogous manner, the compounds of the following Table 1 can be prepared.

Table 1

Ex. A R ² ₆ Hv -5-CO ₂ C ₂ H ₅ -C ₆ H ₂ Mp [° C] Preparation analog Ex. 1 • 2 1 2 6 I * " *) A-Cl-C Z ^- C ₆ Hj , -5-CO ₂ C ₂ H ₅ -C ₆ H ₂ 68-72 2 1 2 7 T * ) 3,5-Cl -FS-OCH (CH ₃ ) JC ₆ H, 2-5-0CH ₃ -C ₆ H ₂ 76-80 2 2 8th T A-Cl-2 -C ₆ H ₃ light brown 2 2-C ₆ H ₃ resin 2 9 T 2, A-Cl ZC ₆ H ₃ 2-5-CO ₂ CH ₂ CO ₂ CH ₃ -Cg 68-75 1 10 I 2, A-Cl z-5-OCH ₃ -C ₆ H ₂ -3,5-Cl ₂ -C ₆ H 72-76 1 11 I 2, A-Cl sH s) 2 -C ₆ H ₃ 2 12 T 2,6- (C ₅ 0) -C ₆ Hv ₃ ) 2-C ₆ H ₃ yellow oil 1 13 T 3- (C ₆ H A- (A-Cl-C ₆ HvO) -C ₆ Hv ₂ CHj) 2-C ₆ H ₃ 2 IA T A- (A-Cl-C ₆ Hv-O-CH ₂ ) -C ₆ Hv , -5-CN-C ₈ H ₂ yellow resin 1 15 T 2, AF ₂ 1-naphthyl 2 16 T 2, A-Cl 2 17 I 2, A-Cl 2 18 I 2, AF ₂ 2 19 T η 2 20 I 2, A-Cl light brown oil 21 T 2, AF ₂ ^H 2 22 I η 23 T (3,5-CF 2A T (3,5-CO 25 T 2, A-Cl 26 T 27 T

3sp. A R ² π hj Mp [° C] Preparation analog Ex. F 2, A-Cl ₂ -S-SOjCH ₃ -Ce 28 I "\ 2 ^" ^C1 OC ₂ H ₅ Cl 1 0 - P - S - / cw- egg H ₅ OCjHs SOjCHj-CO ₂ Cj 29 T 3-COjC ₂ H ₅ -A-Cl-CeH ₃ H ₃ 2 30 T 4-01-3-OCH (CH ₃₎ - C. 2 A-Cl-pyrid-3-yl ' 31 T η 2 2 A-Cl-2-F-5-OCH ₃ -C ₆ H 32 T 2, A-Clj-5-OCH ₃ -C _e Hj 2 33 I 2, A-Cl ₂ -C ₆ H ₃ 1 3A I A-CI-C ₆ H _1n 1 35 T 2, AF ₂ -C ₆ H ₃ hj 2 36 -Cl 2, AF ₂ -S-COjCjHs-Ce eH ₂ 5 37 ti 2, A-C1j-5-C0jCjHs-C 5 38 tt A-Cl-3-C0jC ₂ H ₅ -C ₆ H ₃ H ₃ 5 39 n A-Cl- ₃ -OCH (CH ₃ ) j C ₆ 5 AO η AFC _{6 1} h. 5 al η A-Cl-pyrid-3-yl 5 A2 η 1-naphthyl 5 A3 tt 8-quinolinyl 5 AA π 5 A5 It 5 A6 η 5 A7 ft 5 A8 η 5

Ex. A R ² Fp [ ⁰ C] 2 yellow oil 119-21 Manufacturing analog Bsp. 49 P (OC ₂ H ₅ ) J A-CL ₂ -FS-OCH ₃ -C ₆ H, 128-31 3 50 π A-Cl-C ₆ Hv 112-13 _β Η ₂ 3 51 η 3,5-Cl ₂ -C ₆ H ₃ 181-84 3 52 π 3,5- (CFa) ₂ -C ₆ H ₃ . 175-76 3 53 tl 2, AF ₂ -C ₆ H ₃ yellow 3 0 Oei 54 P (0CH ₃ ) ₂ η η 3 55 π AFC ₆ Hv 106-10 3 0 yy 56 P (OC ₂ Hs) ₂ A-Cl-C _{6-C 6} HvO Hv 125-26 3 0 57 P (OCH ₃ ), 3-C ₆ H ₅ OC ₆ Hv 102-04 3 58 η A- (A-Cl-C ₆ Hv-CH ₂ O) -C ₆ Hv 3 59 tt A-Cl-2-F-5-OCH ₃ -C ₆ H ₂ 3 60 η A-Cl-2-F-5-OCH (CH ₃ ) ₂ -C ₆ H 3 61 π 2, AF ₂ -5-C0 ₂ C ₂ H ₅ -C ₆ H ₂ 3 61 P (OC ₂ Hs) ₂ η 3 63 η 2,4-Cl ₂ -S-CO ₂ C ₂ H ₅ -C ₆ H ₂ 3 64 η 2, A-Cl ₂ -S-CO ₂ CvH ₉ -C ₆ H ₂ 3 65 tl 2, A-Cl, -5-CO ₂ CH ₂ CO ₂ CH ₃ -C 3 0 Il 66 61 P (OCH ₃ ), Tt 2, A-Cl ₂ -5-CO ₂ CH (CH ₃ ) CO ₂ C ₂ H ₅ - 4-Cl-3-CO ₂ C ₂ H ₅ -C ₆ H ₃ 3 3 68 η 4-Cl- ₃ -OCH (CH ₃ ) ₂ -C ₆ H ₃ 3 69 π 4-Cl-pyrid-3-yl 3 70 tt 3-pyridyl 3 0 Il 71 P (OC ₂ Hj) ₂ 4-Cl-pyrid-3-yl 3 72 η 3,5- (CO ₂ CHa) ₂ -C ₆ H ₃ 3 73 η 2,4-Cl ₂ -5-CN-C ₆ H ₂ 3 7A η 2,4-Cl ₂ -5-SO ₂ CH ₃ -C ₆ H ₂ 3

Ex. A 0 R ² Mp [ ⁰ C] Preparation analog Bsp. P (OCH ₃ ), F 75 \ 0Vci _no U \ / UU ₂ Π ₅ 3 0 - P-S η OC ₂ H ₅ 76 η 2, ACl ₂ -S-SO ₂ CH ₂ CO ₂ C ₂ H ₅ -C ₆ H ₂ 3 77 η 2,6- (C ₂ Hs) ₂ -C ₆ H ₃ yellow oil 3 78 η 1-naphthyl 3 79 η 8-quinolinyl. 3 80 η 5-isoquinolinyl 3 81 SCN 1-isoquinolinyl 3 82 A-Cl-2-F-5-OCH (CH ₃ ) ₂ -C ₆ H ₂ yellow A η Oei _, π η α 8A π ^, * + WJ · ₂ - ^ VJOn ₃ -1 «. ₆ ΓΊ ₂ 2, A-Cl ₂ -C ₆ H ₃   A 85 η A-Cl-C ₆ Hv 105-07 A 86 η AFC ₆ Hv A 87 η 2, AF ₂ -C ₆ H ₃ orange oil 4 88 π A-Cl-3-C0 ₂ C ₂ H ₅ -C ₆ H ₃ A 89 η 3-CO ₂ C ₂ H ₅ -C ₆ H ₄ ' A 90 η A-Cl- ₃ -OCH (CH ₃ ) ₂ -C ₆ H ₃ A 91 η 2, A-Cl ₂ -S-CO ₂ CK ₅ -C, H ₂ A 92 η 2, AF ₂ -S-CO ₂ C ₂ H ₅ -C ₆ H ₂ Cl A 93 η \ OV Cl _CH \ / Ln ₃ CO-CH-CO ₂ C ₂ H ₅ B A 9A  <O> -F A CO-CH ₂ -CO ₂ CH ₃ H 0

R ² -13- 249 622 Mp [° C] HersteUg. analog Ex. Ex. A 3,5-Cl ₂ -C ₆ H ₃ A 95 - SCN 3,5- (CO ₂ CHa) ₁ -CeH ₃ A 96 " 3,5- (CFa) ₂ -C ₆ H ₃ A 97 ⁿ 3,5-Cl ₂ -2, AF ₂ -C ₆ H A 98 " AC ₆ H ₅ -O-CeH, A 99 ⁿ 3-C ₆ H ₅ OC ₆ H, A- 100 " A- (A-Cl-C ₆ H, -CH ₂ O) -C ₆ H, A 101 " 1-naphthyl A 102 " 3-pyridyl A 103 " 8-quinolinyl A 1OA "

OC ₂ H ₅

Ό - P = S I

0C ₂ .H ₅

"2,4-Cl ₂ -S-SO ₂ CH ₃ -CH ₂

"2,4-Cl ₂ -S-CN-C ₆ H ₂ O.

Il

P- (OC ₂ H ₅ ) ₂ 2,4-Cl ₂ -5-OCH, -C, H ₂

T4-Cl-2-F-5-OCH, -C, H-

I I T.

OP (OC ₂ H ₅ ) ₂

0 ι

3-CF ₃ -C ₅ H ₄

4-Cl-3-OCH ₃ -CgH ₃ 4-01-3-CO ₂ C ₂ H ₅ -CgH ₃

P (OC ₂ H ₅ ) ₂ 3-CO ₂ CH (CH ₃ ) ₂ -CgH ₄

16A-66

light brown resin

light brown resin

1 1 2

119-122 3 yellow oil 3

light brown3 resin

Eg A 'R ² · Fp ^ C? Berstellg.

Analcg Ex.

117 P (OC ₂ H ₅ ) ₂ 3-CF ₃ -C ₆ H ₄ 98-101 3

118 SCN 3-CF, -C _c H. 'light brown 4

, ^{3 6 4} resin

119 P (OC ₂ H ₅ ) ₂ 4-Br-3-CO ₂ C ₂ H ₅ -CgH ₃ 3

120 P (OC ₂ H ₅ ) ₂ 4-Br-3-CO ₂ CH (CH ₃ J ₂ -C ₅ H ₃ .3

121 SCN 4-Br-3-CO ₂ C ₂ H ₅ -C ₆ H ₃ yellow oil 4 O

122 P (OC ₂ H ₅ J ₂ 4-CF ₃ -C ₆ H ₄ 148-150 3 O

123 P (OC ₂ H ₅ J ₂ 4-Cl-3-OCH ₃ -CgH ₃ 120-121 3

124 P (OC ₂ H ₅ ) ₂ 4-Cl-2-F-5-OCH ₂ CO ₂ CH ₃ -CgH ₂ 3

? ί

125 P (OC ₂ H ₅ ) ₂ 4-Cl-2F-5-O-CH-CO ₂ C ₂ H ₅ -CgH ₂ 3

O - CH ₃

126 P (OCH ₃ ) ₂ 4-Cl-2F-5-O-CH-CO ₂ C ₂ H ₅ -CgH ₂ 3

127 SCN 4-01-2F-S-O-CH-CO-C-He-C ^ H, yellow 4

ζ / 5 ö ί _oil

128 SCN 4-Cl-2F-5-O-CH_-CO_CH, -C, H, yellow 4

* * ^ä ° ^Δ oil

♦) T = -N ___ I

Example 129 Vinyl O- [2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-oxo-2,3,4,5,6,7-hexahydro-1H-isoindol-1-yl] - phosphonate 8.6 g (20 mmol) of 2- (4-chloro-2-fluoro-5-methoxy-phenyl) -3-diethoxy-phosphoryl-4,5,6,7-tetrahydroisoindolinon (Bsp.49) are 4h at 10O ⁰ C stirred vigorously in 80 ml of 10% hydrochloric acid. The aqueous hydrochloric acid is distilled off at 50 ° C. in a water-jet vacuum. The resinous residue is dissolved in 100 ml of 5% potassium hydroxide solution and shaken with 50 ml of ethyl acetate. The water phase is brought to pH 2 with ice-cooling with concentrated hydrochloric acid and the precipitate is filtered off with suction and dried. This gives 6.2 g (77% of theory) of monoethyl [2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-oxo-2,3,4,5,6,7, - hexahydro-IH-isoindol-1-yl] -phosphonate in the form of colorless crystals with mp 124-126 ⁰ C.

Example 130.

Monoethyl [2- (4-chloro-2-fluoro-5-methoxy-phenyl) -3-oxo-2,3,4,5,6 _/ 7-hexahydro-1H-isoindol-1-yl] -phosphonate potassium salt

8.5 g (20 mmol) monoethyl [2- (4-chloro-2-fluoro-5-methoxy-phenyl) -3-oxo-2,3,4,5,6,7-hexahydro-IH-isoindole-1. yl] -phosphonate (Ex: 129 and 1.12 g (20 mmol) of potassium hydroxide are stirred for 30 minutes in 100 ml of methanol at 20 ° C. The solvent is removed by evaporation, and the residue is dried, yielding 9.4 g (100% of theory). Th.) Monoethyl [2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-oxo-2,3,4,5,6,7-hexahydro-IH-isoindol-1-yl] - phosphonate potassium salt in the form of pale yellow crystals which melt at 151-153 ° C with decomposition.

Step Example! 131 [2- (4-chlorophenyl) -3-oxo-2,3,4,5,6,7-hexahydro-1H-isoindol-1-yl] -phosphonic acid 19.2 g (0.05 mol) 2- (4 -Chlorophenyl) -3-diethoxyphosphoryl-4,5,6,7-tetrahydroisoindolinone (Ex. 50) is concentrated in 130 ml of conc. Hydrobromic acid at 100 ⁰ C stirred, concentrated by rotary evaporation and dried at 50 ⁰ C in a high vacuum. This gives 16.1 g (98% of theory) of [2- (4-chlorophenyl) -3-oxo-2,3,4,5,6,7-hexahydro-IH-isoindol-1-yl] - phosphonic acid in the form of colorless crystals having mp. 103- 106 ⁰ C.

Example 132 [2- (4-Chlorophenyl) -3-oxo-2,3,4,5,6 _/ 7-hexahydro-1H-isoindol-1-yl] phosphonic acid dipotassium salt Dissolve 16.4 g (0.05 mol ) [2- (4-chlorophenyl) -3-oxo-2,3,4,5,6,7-hexahydro-IH-isoindol-1-yl] -phosphonic acid (Ex.131) and 5.6 g (0, 10 mol) of potassium hydroxide in 200 ml of methanol and stirred for 30 min at 20 ⁰ C. The methanol is distilled off and the residue is dried. This gives 22.0 g (100% of theory) of [2- (4-chlorophenyl) -3-oxo-2,3,4,5,6,7-hexahydro-IH-isoindol-1-yl] -phosphonic acid Form of yellow crystals, melting at 188-190 ⁰ C with decomposition.

Example 133 Ethyl [2- (4-chloro-2-fluoro-5-methoxy-phenyl) -3-oxo-2,3,4,5,6,7-hexahydro-1H-isoindol-1-yl, methyl-phosphinate

9.9 g (0.03 mol) of 3-chloro-2- (4-chloro-2-fluoro-5-methoxyphenyl) -4,5,6,7-tetrahydroisoindolinone and 4.1 g (0.03 mol) of diethyl methanephosphonate together with 10 mg of potassium iodide for 20 min at 120 ⁰ C heated. The solid obtained is boiled up with 100 ml of ether and filtered with suction. This gives 11.4 g (95% of theory) of ethyl [2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-oxo-2,3,4,5,6,7-hexahydro -IH-isoindol-1-yl, methyl] -phosphinate in the form of colorless crystals with mp. 180-183 ° C.

Example 134 [2- (4-Chloro-2-fluoro-5-methoxy-phenyl) -3-oxo-2,3,4,5,6,7-hexahydro-1H-isoindol-1-yl], methyl phosphinic acid 12.1 g (0.03 mol) of ethyl [2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-oxo-2,3,4,5,6,7-hexahydro-IH Isoindol-1-yl, Jmethyl-phosphinate (Ex. 133) is stirred for 3 h at 100 ⁰ C in 120 ml of 20% hydrochloric acid and concentrated by rotary evaporation. The remaining resin is dissolved in 100 ml of 10% potassium hydroxide solution and shaken with 50 ml of ethyl acetate. The water phase is concentrated under ice-cooling with conc. Hydrochloric acid brought to pH 2 and the precipitate was filtered off with suction and dried. This gives 10.4 g (93% of theory) of [2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-oxo-2,3,4,5,6,7-hexahydroxy). IH-isoindol-1-yl], methylphosphinic acid in the form of colorless crystals with mp. 153-155 ° C.

Example 135

[2- (4-chloro-2-fluoro-5-methoxy-phenyl) -3-oxo-2,3,4,5,6,7-hexahydro-1H-isoindol-1-yl], methyl-phosphinic acid Potassium salt 7.5 g (0.02 mol) of [2- (4-chloro-2-fluoro-5-methoxy-phenyl) -3-oxo-2,3,4,5,6,7-hexahydro-IH-isoindole 1-yl], methyl-phosphinic acid (Ex. 134) and 1.12 g (0.02 mol) of potassium hydroxide are dissolved in 100 ml of methanol and stirred at 20 ⁰ C for 20min. The solvent is removed and the residue is dried at 50 ^° C. under high vacuum. This gives 8.3 g (100%, of theory) of [2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-oxo-2,3,4,5,6,7-hexahydro -IH-isoindol-1-yl], methyl-phosphinic acid potassium salt in the form of pale yellow crystals which melt at 174-177 ° C with decomposition.

Example 136 2- (4-Chloro-2-fluoro-5-methoxy-phenyl) -3-diphenylphosphoryl-4,5,6,7-tetr, ahydroisoindolinone 9.9g (0.03mol) 3-chloro-2 ( 4-chloro-2-fluoro-5-methoxyphenyl) -4,5,6,7-tetrahydroisoindolinone and 6.9 g (0.03 mol) of diphenylphosphinous acid ethyl ester is warmed to 12O ⁰ C with 20 mg of potassium iodide for 30 min. The remaining residue is boiled with 150 ml of ether and filtered with suction. This gives 13.4 g (90% of theory) of 2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-diphenylphosphoryl-4,5,6,7-tetrahydroisoindolinone in the form of colorless crystals with mp 207-209 ⁰ C.

Continuation Table 1

Ex. AR ² Fp / ⁵ C / preparation

analog Ex.

137 -P (OH) -4-Cl-2-F-5-CCH, -C, H. , T 31

0 -

138 -P (OK) ₂ "·

: 139 -P (OC ₂ H ₅ ) 4-Br-C ₆ -H ₄ 128-131 3

140 -P (OC ₂ H ₅ V ₂ 4-J-CgH ₄ 150-153 3

141 -ΡΗΧΗ "126-128 129

CH O

142 -P-CK 4-Cl-C ₆ H ₄ 151-153 130

OC ₂ H ₅ O

143 -P (OH) ₂ 4 -Br-CgH ₄ 143-145 131

144 -P-OC ₂ H ₅ 4-Cl-C ₆ H ₄ ¹³³

ca,

³ * m

Production anlago Ex.

1 4 6 -P-OC _n H

ι CH-

₂ H ₅

3-C0-C_H_c-4-Cl-C, H_O ZZD DJ

133

-P-OH CH,

-P-OK CH-,

-P (CH,) -

 5 Δ

-P (CH ₃ ) ₂

4-Cl-C ₆ H ₄

4-Br-C ₆ H ₄

.4-0.-2-F-S-OCH-J-C-H.,

JOZ 134 134 135 135 136

136 136

156 -

- ³ T ^ ₅

CH ₃

0 -PC ₆ H ₅

CH ₃ 0 II P-OCH,

ι *

OH

-P-OK CCH,

4-Cl-O-H. 64

4-Cl-2-F-5HXH, -C _r H

4-Br-C ₆ H ₄

4-Cl-2-F-5-CCH, -C _r H

4-Cl-C ₆ H ₄

4-Br-C.H. 6 136 136

129

129 129

130

130 130

Ex. AR ² Fp [ ⁰ C] prepared analog Ex.

4-Cl-3-CO ₂ C ₄ H _g -C ₆ H ₃ resin 3

4-F-3-CO ₂ C ₂ H ₅ -C ₆ H ₃ 3

4-Br-3-CO_C-H _c -C 3 H

2 2 5 ο j

2,4-F _o -5-C0 _o C _o Hc-C, -H _o 3

2 ZZ 5 b Z

4-C _1-3 -CO C ₃ H ₅ -C ₆ H ₃ 3

4-Br-3-C0 _o C.H_-C _c H-3

ZiI bJ

4-F-3-CO C H -O, .H- 3

2 2 5 6 3

4-CH - 3-CO ₀ C ₀ Hc-C ^ H. 3

3 currently 5 DJ

4-OC H, -3-C0, C, H, -C, H, 3

2 b 2 2 5 6 3

4-OCH ₃ -S-CO ₂ C ₂ H ₅ -C ₆ H ₃ 3

2-F-4-Cl-5-C0 _o C _o H _c -C _; , H _o 3

ZZd ο Ζ

4-F-3-CO ₂ C ₂ H ₅ -C ₆ H ₃ 3

4-01-3-CO ₀ C ₀ Hc-C ^ H, 3

ZZd dj

4-Br-3-C0 _o C _o Hc-C _c H_ 3

2 2 5 6 3

4-F-3-CO ₂ C ₂ H ₅ -C ₆ H ₃ 3

4-Cl-S-CO ₀ C ₀ Hc-C ^ H- 3

2 ZD DJ

4-Br-3-C0 _{0 0} Hc C-C _c H ₀ 3

2 2 5 6 3

4-Br-3- [CO ₂ CH (CH ₃ JCO ₂ C ₂ H ₅ JC ₆ H ₃ 3

4-Cl-3- [CO ₂ CH (CH ₃ JCO ₂ C ₃ H ₅ JC ₅ H ₃ 3

4-F-3- [CO CH (CH ₃ ) CO ₂ C ₂ H ₅ JC ₆ H ₃ 3

2,4-F ₂ -5- [CO ₂ CH (CH ₃ pO ₂ C ₂ H ₅ JC ₆ H ₂ 3

4-Br-3-C0-CH _o CF_-C _c H-3

2 2 j D j

4-Cl-3-CO _or CH _o CF.-CH. 3

2 2 j D ο

4-F-3-C0-CH- _O- CF, -C- _I , H- _O- 3

2 2 JDJ

4-F-3-C0 _o CH _o CF.-C, H _o 133

2236-3

162 P (OCH 3> 2 163 It 164 Il 165 O H 2 H ) 166 it 167 Il 168- Il 169 η 170 II 171 H 172 η ο 173 P [igh (CH ₃ J ₂ 174 Il 175 ti 176 O Il P (Oc ₄ V ₂ 177 Il 178 Il O Il 179 Il P (Oc ₂ V ₂ 180 Il 181 η 182 M 183 π 184 0 Il P (OCH 3> 2 185 Il O Il 186 P-OC ₂ ^Η 5 CH

Ex. AR Fp [ ⁰ C] produced . analog Ex.

O //

4-F-3-C0 _o C _o Hc-C _ft H, 133

2 ZD DJ

4-Br-3-C0 _o C _o H -C H. 133

2 2b DJ

2,4-F -3-C0 ₀ C ₀ H _I -C ₍ .H ₀ 133

2 2 2 D b J

2-F-4-Cl-5-COO ₀ C ₀ H _c -C, H ₀ 133

2 2 D b 2

4-01-3- [CO ₂ CH (CH ₃ ) -CO ₂ C ₃ H ₅ ] -C ₆ H ₃ '133

4-Br-3- [CO ₂ CH (CH ₃ ) CO ₂ C ₂ H ₅ JC ₆ H ₃ 133

4-F-3- [CO ₂ CH (CH ₃ ) CO ₂ C ₂ H ₅ JC ₅ H ₃ 133 '

2,4-F ₂ -S- [CO ₂ CH (CH ₃ JCO ₃ C ₂ H ₅ ] -C ₆ H ₂ 133

4-C 1-3 -CO C, H, -C, H, 136

2 Z ο ο ο

4-F-3-CO_C_H _c -C H_ 136

2 2 5 6 3

4-Br-3-C0 _o C _o H _c -C _c H_ 136

2 2DbJ

2,4-F ₀ -S-CO ₀ C ₀ Hc-C ^ H ₀ 136

2 2 2 ο ο 2

4-Br-3- [CO ₂ CH (CH ₃ ) -CO ₂ C ₂ H ₅ ] -C ₆ H ₃ 136

0 // PC ₆ H ₅ 4-Cl-3-CO ₂ C ₂ H ₅ -C ₆ H ₃ 136

4-Br-S-CO ₀ C ₀ Hc-C ₁ -H ^ 136

2 2 D DO

l, 4-F ₀ -3-C0 ₀ C ₀ H, -C, H ₀ 136

2 ZB BB Z

187 P-OC ₀ Hc I 2 D 188 η 189 M 190 π 191 tt 192 Il 193 " 194 M 195 196 0 P (C ₆ H ₅ ) ₂ M 197 Il 198 It 199 Il

CH ₃ (OC ₂ H ₅ 201 Il 202 M 203 Il O Ii ρ 204 Il 205

4-Cl-3- [cO ₂ CH (CH ₃ J-CO ₂ C ₃ H ₅ JC ₆ H ₃ 136

₂ C ₃ H ₅ JC ₆ H ₃

4-Cl-2F-5- <OCH ₂ C = C) -C ₆ H ₂ 124-127 3

4-Br-2F-5-0CH_-C _i -H _o 146 3 3 ο Z

C. Biological examples

The damage of the weed plants or the crop plant compatibility was scored according to a key in which the effectiveness is expressed by values of 0-5. Where: t ^:

0 = no effect or damage 1 = 0-20% effect or damage

2 = 20-40% effect or damage

3 = 40-60% effect or damage

4 = 60-80% effect or damage

5 = 80-100% effect or damage 1. weed effect in pre-emergence

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weed plants were placed in sandy loam soil in plastic pots (O = 9 cm) and covered with soil. The compounds according to the invention formulated in the form of wettable powders or emulsion concentrates were then applied to the surface of the cover soil as aqueous suspensions or emulsions having a water application rate of 600 l / ha in different dosages.

After the treatment, the pots were placed in the greenhouse and kept under good growth conditions for the weed plants (temperature 23 plus / minus 1 ⁰ C, relative humidity 60-80%).

The optical assessment of the plant or run-in damage occurred after emergence of the test plants after a

Trial period of 3-4 weeks compared to untreated controls.

The scores in Table 2 show that the compounds of the present invention have good herbicidal pre-emergence activity

against a wide range of grass weeds and weeds.

Table 2 Preliminary action of the compounds of the invention

Dose kga.i./ha

herbicidal activity SIA

LOM

ECG

2.5 2.5 2.5 2.5 -2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2 , 5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5

5 5 3 5 4 3 5 5 4 5 4 2 3 4 5 5 4 3 5 5 2 5 5 5 5 1 4 2 5 5 5

5 5 4 5 5 4 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 3 5 5 5 5 1 5 3 5 5 5

5 5 5 5 5 5 5 5 5 5 4 5 5 4 5 5 5 4 5 3 5 5 5 5 5 5 4 5 5 5 5

5th

Abbreviations:

Sinapisarvensis Chrysanthemum segetum Lolium multiflorum Echinochloa crus-galli Active substance

2. weed effect postemergence

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds were placed in sandy loam soil in plastic pots (= = 9 cm), covered with soil and grown in the greenhouse under good growth conditions. Three weeks after the

Sowing, the test plants were treated in the three-leaf stage.

The compounds according to the invention formulated as wettable powders or emulsion concentrates were sprayed onto the green parts of the plant in various dosages with a conversion rate of 600 l / ha and after about 3-4 weeks life of the test plants in the greenhouse under optimum growth conditions (temperature 23 plus / minus 1 ⁰ C, relative humidity 60-80%) the effect of the preparations optically scored compared to untreated controls.

The compounds according to the invention also have a good herbicidal activity against the broad spectrum postemergence

economically important grass weeds and weeds (Table 3).

Table 3 Follow-up action of the compounds according to the invention

LOM ECG

4 2

5 5 5 4 3 2 3 3 5 5 1 2

3 5

4 2

4 2 1 2

5 5 5 4 5 2 5 5 5 5 5 5 5 4

4 1.

5 2 5 2 5 5 5. 5

Abbreviations: s.Tab.2

3. crop compatibility

In further experiments in the greenhouse, seeds of a larger number of crops were grown in pots in sandy

Clay floor designed and covered with earth.

Part of the pots were treated immediately as described under 1.; the rest were placed in the greenhouse until the plants had developed two to three true leaves and then with the substances of the invention in different

Dosages as described under 2. sprayed.

Four to five weeks after the application and life in the greenhouse was determined by optical Bonitur that compounds of the invention dicotyledonous crops such. As soybean, cotton, oilseed rape, sugar beets and potatoes in pre- and post-emergence even at high doses of active ingredient undamaged. In addition, some substances also protected Gramineae crops such. As barley, sorghum, corn, wheat or rice. The compounds of formula I thus have a high selectivity in application and Bekämfpung of undesirable plant growth in agricultural

. important cultures.

Ex. dose herbicidal action C kga.i./ha SIA 3 5 2.5 4 4 49 2.5 5 5 3 2.5 5 4 1 2.5 5 4 8th 2.5 4 5 4 2.5 5 4 67 2,5, 3 4 87 2.5 3 3 109 2.5 5th 3 114 2.5 4 5 125 2.5 5 5 129 2.5 5 2 131 2.5 5. 2 132 2.5 5 5 133 2.5 5 5 134 2.5 5 3 136 2.5 5 2 139 2.5 2 1 142 2.5 5 1 143 2.5 5 1 144 2.5 4 5 204 2.5 , 5 5 205 2.5 5

Claims (2)

claims: 1. A herbicidal center, characterized in that it is a compound of formula I. H "" A (D contain, in which (C ₁ -C ₄ ) Alkyl; Phenyl, naphthyl, pyridyl, quinolinyl or isoquinolinyl, where these radicals one to four times, preferably one to three times, by identical or different radicals of the group halogen, hydroxy, (Ci-C ₄ ) alkoxy, (C ₁ -C ₄ J -alkoxy, (C ₃ -C ₆₎ Cycloaikoxy, (C ₃ -C ₆₎ Aikenyloxy, (C ₃ -C ₆₎ alkynyloxy, halo (dC ₄₎ alkyl, halo (C! _-C4) alkoxy, halo ( C ₃ -C ₆ ) alkenyloxy, halo (C ₃ -C ₆ ) alkynyloxy, (C ₁ -C ₄ ) alkylthio, (C ₁ -C ₄ ) alkylsulfinyl, (C ₁ -C 8 -alkylsulfonyl, where in the latter three radicals the alkyl group may be substituted by (C ₁ -C ₄₎ alkoxycarbonyl, NO _2, CN, halogen (dC ₄₎ alkyl, cyano (dC ₄₎ alkyl, phenoxy, phenoxy (dC ₄₎ alkyl, phenyl (Ci-C ₄ ) alkoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, where the six last-mentioned radicals in the phenyl ring are substituted by up to three times by halogen, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) -alkoxy or (C ₁ -C ₄ ) -alkoxycarbonyl or by a remainder of the formulas -CXR ³ , -0-Ρ (ΥΪ1 ⁴ ) _ο or -Z- (CH) -CXR ³ can be substituted
O, S or NR ⁶ , independent of each otherO or S ^,! Hydrogen, (C ₁ -C ₁₂ ) AlkYl, up to 6 times by halogen and / or up to two times by (C ₁ -C ₄ J -OXOXY, (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ ) alkoxy (dC ₄ alkoxy) carbonyl, (C ₁ -C ₄₎ AIkYItIIiO, (d-CJAIkylsulfinyl, (C -] - C ₄₎ alkylsulfonyl, (dC ₄₎ alkylamino, di (C ₁ -C ₄₎ alkylamino, Furyl, tetrahydrofuryl, benzofuryl, phenyl, phenoxy, benzyloxy, wherein the phenyl rings may be substituted up to three times by halogen, (C ₁ -C ₄ ) AIkYi or (Ci-C ₄ ) alkoxy, (C ₃ -C ₆ -cyClOalkyl, (C ₃ -C ₆ ) alkenyl, cyclohexenyl, (C ₃ -C ₆ ) alkynyl, phenyl which may be substituted up to three times by halogen, (C ₁ -C ₄ ) alkyl, (C ₁ - C ₄ ) AIkOXy or (C ₁ -C ₄ alkoxy) -CaTbOnYl; ^: p7 a remainder of the formula -ji = ( or a cation usable in agriculture; (C ₁ -C ₄ ) alkyl, Hydrogen, (C ₁ -C ₄ ) alkyl, Is hydrogen, (C 1 -C ₄ ) alkyl which together with R ³ and the nitrogen atom linking these radicals can form a five- to seven-membered heterocyci which contains as ring members one or two radicals of the group-O-, -S-, NR ⁵ and up to triple may be substituted by (Ci-C ₄ ) alkyl,
R ⁷ , R ⁸ = independently of one another (C ₁ -C ₄ ) AlKyl, (C ₃ -C ₆ ) CyClOalkyl or together (C ₂ -C ₇ ) alkylene chain;
A = a remainder of the formulas -PR ⁹ or '-NGS, J ¹⁰ R ⁹ , R ^{10 are} independently (C ₁ -C ₄ ) alkyl, phenyl or benzyl, both up to two times is halogen, (C ₁ -C ₄ ) alkyl, CF ₃ or (C ₁ -C ₄ ) Al koxy substituted η can; (C ₁ -C ₄ ) alkoxy; (C ₁ -C ₄ ) -alkylthio; OH, SH, OM or SM, where M is an agriculturally usable cation, or a radical of the formula -NR ¹¹ R ¹² , R ¹¹ , R ^{12 are} independently hydrogen; (C ₁ -C ₆ alkyl) phenyl or benzyl, both up to two times by halogen, (C ₁ -C ₄ ) AlkYl, CF ₃ or NO ₂ may be substituted, or R ¹¹ and R ¹² together with the adjacent N-atom of a five- to six-membered heterocyclo which as ring members one or two Radicals of the group -O -, - S or NR ⁵ - may contain and which may be substituted up to three times by (C ₁ -C ₄ ) alkyl; m = 0.1 or 2 and η = 1,2 or 3 mean in addition to extenders and / or surface-active agents. Herbicidal agent according to Claim 1, characterized in that in the compounds of the formula I R ² = phenyl, pyridyl, both 1 to 3 times by (C ₁ -C ₄ ) AlkYl, which is up to three times by Halogen, may be substituted by F, Cl, Br, (Ci-CJ-alkoxy, which may be up to nine times substituted by fluorine and / or chlorine, by (CiC ^ alkylthio, -CO-XR ³ or are substituted
Χ, Υ, Ζ = OoderS, R ³ = (C ₁ -C ₆ ) alkyl, (C ₁ -C ₄ alkoxycarbonyl) C ₁ -C ₆ alkyl or (C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ -alkyl) A = a remainder of the formulas -PR ⁹ or -HCS, R ⁹ , R ¹⁰ = independently of each other (C ₁ -C ₄ ) AlkYl; Phenyl, or benzyl, both of which up to two times by halogen, (C ₁ -C ₄₎ -alkyl, CF ₃ or (Ci-C ₄₎ alkoxy substituted can; (C ₁ -C ₄ ) alkoxy; (C 1 -C ₄ ) -alkylthio; OH, SH, OM or SM, where M is an agriculturally useful cation, or a radical of the formula -NR ¹¹ R ¹² and R ¹¹ , R ¹² = independently of one another hydrogen; (C ₁ -C ₆ ) -alkyl; Phenyl or benzyl, both of which may be substituted by up to three times by halogen, (C ₁ -C ₄ ) alkyl, CF ₃ or NO _2, or R ¹¹ and R ¹² together with the adjacent N atom represent a five- to six-membered heterocycle which may be substituted with Ring members may contain one or two radicals of the group -O -, - S- or -NR ⁵ - and which may be substituted up to three times by (C ₁ -C ₄ alkyl group; η = 1, m = O or 1. 3. A herbicidal composition according to claim 1, characterized in that in the compounds of formula I. R ² = phenyl, which is 1 to 3 times by (C ₁ -C ₄ ) AlkYl ^ aSbISZU triply by halogen may be substituted, F, Cl, Br, (C ₁ -C ₄₎ -alkoxy, which can be up to trisubstituted by fluorine and / or chlorine, (Ci-C ₄₎ alkylthio, -CO-XR ³ or -Z- CH-GO-XR ³