CS268818B2 - Herbicide and method of its effective substances production - Google Patents

Abstract

Die Verbindungen der Formel I worin

• R¹ - Alkyl, R^{2 -} Phenyl, Naphthyl, Pyridyl, Chinolinyl oder Isochinolinyl bedeutet, die substituiert sein können, einen Rest der Formeln -C(O)-XR³, -OP(Z) (YR⁴)₂ oder -Z-(CHR⁵)₂-CO-_XR3
• A - einen Rest der Formeln Y
  -PR⁹R¹⁰ oder -NCS und m - 0, 1 oder 2 bedeuten, besitzen vorteilhafte herbizide Eigenschaften gegenüber mono- und dikotylen Schadpflanzen.

Description

The invention also relates to a herbicidal composition which contains the novel tetrahydroisoindolinones as active ingredient. The invention further relates to a process for the production of these novel tetrahydroisoindoloneones as well as to their use in plant protection.

Certain tetrahydroisoindelinone derivatives are known to have herbicidal properties (cf. European patent application 40 849 and European patent application 40 849 and European patent application 41 256).

We have now found novel tetrahydroisoindolinones with advantageous horbicidal effects.

Accordingly, the present invention provides a herbicidal composition which comprises as active ingredient at least one 4,5,6,7-totrahydroisoindolinone of the formula I '

/ I / in which

R is 4-chlorophonyl, 4-bromophenyl, 4-iodophonyl, 2,4-difluorophenyl, 2,4-dichloro-5-mothoxyphenyl,

4-chloro-2-fluoro-5-methoxyphonyl, 4-bromo-2-fluoro-5-methoxyphenyl, 2,4-chloro-5-methoxycarbonylphenyl, 4-chloro-3-ethoxycarbonylphenyl, 4-chloro -2-fluoro-5-isopropoxyphonyl, 4-bromo-3- (propexycarbonyl) phenyl, 4-chloro-2-fluoro-5-propargyloxyphenyl, 4-chloro-2-fluoro-5- (1-ethoxycarbonylathoxy) phenyl or 4-chloro-2-fluoro-3- (1-ethoxycarbonylethoxy) phenyl and

A is imidazol-1-yl, 1,2,4-triazol-1-yl, thyocyanato, pyrrolyl or

where

R ⁹ and R ¹⁰ are, independently of each other, methoxy, ethoxy, hydroxy, -OK, methyl, phenyl or butoxy.

Compounds of Formula I may be present as pure ether stereoisomers or mixtures thereof. All of these atheroisomeric forms are within the scope of the present invention.

Of the above compounds, those compounds of formula I are preferred wherein r 2 is 4-chlorophonyl, 2,4-difluorophenyl,

2,4-dichloro-5-methoxyphenyl, 4-chloro-2-fluoro-5-methoxyphenyl, 2,4-dichloro-5-ethoxycarbonylphenyl,

4-chloro-3-ethoxycarbonylphenyl, 4-chloro-2-fluoro-5-isoprepoxyphonyl or 4-chloro-2-fluoro-5- (1-ochoxycarbonylethoxy) phenyl and

A is imidazol-1-yl, 1,2,4-triazol-1-yl, thiocyanato pyrrolyl or formula

CS 268 818 B2 where

R 6 are independently of each other a non-methoxy group or an ethoxy group.

Further preferred compounds are those compounds of formula (I) wherein:

R is a 4-chlorophenyl, 4-bromophenyl, 4-iodophonyl or 4-chloro-2-fluoro-5-methoxyphenyl group and

Λ dream group formula

where

10

R and R are, independently of one another, a hydroxyl group, an -OK group, an ethoxy group, a non-ethyl group or a phenyl group.

Another object of the present invention is to provide a compound of formula (I) which consists of:

R ¹²

N -

/ П / in which

R ² nd abovementioned meaning and snanená nucleofugic skupimu as Aton

R ^{12 of} halogen, tosyl or nyl, acts as a compound introducing the radical A of the general formula

H -

M - SCN nsbo

in which

R ¹ snanená alkyloveu group having 1 to 4 carbon atoms,

R @ ¹⁰ and R @ ¹⁰ are as defined above

The significance of synbol A of the group

СЗ 268 818 В2

M represents a cation cation, preferably a lead cation, a potassium cation or a sodium cation, and the obtained foophonic nobo phosphinic acid steroids are optionally partially or completely hydrolyzed. .

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

The reaction of compound of formula II with trlesteren phosphorous acid, phosphonous acid diester * optionally monoeeterem phosphonous acid of the formula R f -Q-PR-R ¹⁰ is preferably carried out without a solvent at temperatures of 50 and 140 NOZI ^e C, optionally with catalysis by potassium iodide. The phosphonic or phosphinic acid esters obtained can be converted into phosphonic or phosphinic acids by customary methods. Again, these are converted into the corresponding salts or amides of phosphonic or phosphinic acid by conventional methods.

The reaction of the compounds of the formula II with the thiocyanate of the formula M-SCN is carried out in an inert organic solvent such as toluene, acetone or also in dimethylformamide at temperatures between 0 and 100 ° C, preferably at 50 to 80 ° C.

Tetrahydroisoindolinones of the formula II are, in the case where R is chlorine, partly known from DE-OS 28 31 770 and European patent applications 40 849. Other compounds of the formula II can be prepared in a simple manner from 3-hydroxy-3,5,6, 7-tetrahydroisoindolinones of the general formula III with a halogenating agent such as thionyl chloride in a conventional manner (cf. German patent application P 35 33 442.8).

Compounds of formula III

/ III / in which

They are also known compounds (DE-OS 28 31 770) or can be prepared in a simple and known manner from the 3,4,5,6-tetrahydrophthalhalides of the formula IV by reduction with a reducing agent such as sodium borohydride (cf. Rocz. Chem., 49, 1671 (1975)).

Compounds of formula IV

CS 268 818 B2

In which

H ²

has the above meaning,

(IV) can again be prepared by conventional methods from 3,4,5,6-tetrahydrophthalic anhydrides and the corresponding amines. '

The compounds of the formula (X) according to the invention find an excellent herbicidal activity against a wide spectrum of economically important monocotyledonous and dicotyledonous weeds. whether the active substances are applied before sowing, pre-emergence or post-emergence.

Thus, for example, the following monocotyledonous weeds such as deaf oats (Avena fatua), foxtail (Alopecurue op ·), rye (lolium sp.), Shear (Setaria sp ·), dew (Digitaria sp.), Sorghum halepense, Echinochloa sp., Agropyron sp., Cynodon sp., Phalaris sp., And dicotyledonous weeds such as deadnet (Lamium sp.), Speedwell (Vsronica) sp.), Bedstraw (Galim sp.), Chickweed (Stellaria sp ·), Chamomile (Matricaria ep.), Poppy (Papaver sp.), Cornflower (Centaurea sp.), Kindweed (Amaramthus ep ·), Petour (Galinsoga sp.) .), pheasant (Mercurialis sp ·),

Sida sp.

Abutiloa sp ·, Ambrosia sp ·, beet (Xanthiun sp.), Thistle (Cirsiun sp.), Wormwood (Artomisia ep.), Hundred (Runex sp ·), bindweed (Cenvolvulus sp.), Binder (Iponoea sp.), mustard (Sinapie ep.),

When the compounds of the invention are applied to the soil surface prior to germination, either the emergence of pleural germinate plants is completely prevented, or the weeds grow up to the stage of the cotyledon, but then their growth stops and finally dies completely after three to five weeks. *

When the active substances are applied to the green parts of the plants during post-emergence application, the growth also stops drastically after treatment and the weeds remain at the growth stage they were at the time of treatment or die more or less rapidly after a certain time, the use of the novel compositions according to the invention can eliminate the very early and persistent competition of weeds which are detrimental to crop plants.

Although the compounds of the invention have excellent herbicidal activity against monocotyledonous and dicotyledonous weeds, crop plants of economically important crops such as wheat, barley, rye, rice, corn, sugar beet, cotton and soybean only negatively or even at all. is therefore well suited for selective control of undesirable plant growth in agricultural crops ·

In addition, the compounds according to the invention have the ability to control the growth of crop plants. These substances interfere with the metabolism inherent in plants and can therefore be used to facilitate harvesting, such as to induce desiccation, absoioe as well as to inhibit growth. The substances are also suitable for general regulation and suppression of undesirable vegetative growth without killing the plants. Suppression of vegetative growth is of great importance for many monocotyledonous and dicotyledonous crops, as this will reduce or prevent plant lodging.

The compositions of the invention may be used as wettable powders, emulsifiable concentrates, sprayable solutions, dusts, mordants, dispersions, granules or microgranules in the form of conventional preparations.

Wettable powders are uniformly dispersible water formulations which contain, in addition to the active ingredient, a wetting agent, in addition to a diluent or an inert substance, for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, alkyl or alkylphenylsulfonates and dispersing agents such as sodium ligninsulfonic acid, sodium 2,2 '-dinaftylmethan ^{6.6-disulfonic} acid, sodium dibutylnaphthalenesulfonic acid, or the sodium salt oleylmethyltaurinu. They are prepared in the usual way, for example by grinding and mixing the ingredients ·

Emulsifiable concentrates are prepared, for example, by dissolving the active ingredient in an inert organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or else in aromatic hydrocarbon feedstocks or hydrocarbons with the addition of one or more emulsifiers. As emulsifiers, for example, calcium salts of alkylarylsulfonic acid, such as calcium salts of dodecylbenzenesulfonic acid, or non-ionic emulsifiers such as fatty acid polyglycyl esters, alkylaryl polyglycol ethers, polyglycol ethers of fatty alcohols, condensation products of propylene oxide and ethylene oxide, fatty alcohol condensate glycol esters, acids, polyoxyethylene sorbitol esters of fatty acids or polyoxethylene sorbitol esters.

Dusts are obtained by grinding the active ingredient with finely dispersed solids such as talc, natural clays such as kaolin, bentonite, pyrophyllite or diathite.

Granules can be obtained either by spraying the active ingredient on an adsorptive, granulated inert material or by applying the active ingredient concentrates with adhesives, for example polyvinyl alcohol, sodium polyacrylic acid or also mineral oils

CS 268 818 B2 to the surface of carrier substances such as sand, kaolinite or granulated inert material. Likewise suitable active substances can be processed in the manner customary for the production of granular fertilizers IV, optionally mixed and fertilized.

For wettable powders, the active compound concentration is, for example, between 10 and 90% by weight, the remainder being up to 100% by weight consisting of the abovementioned additives used in such compositions. Emulsifiable concentrates may also contain the active ingredient in a concentration of from about 5% to about 80% by weight. Powder formulations usually contain 5 to 20% by weight of the active ingredient, sprayable solutions of about 2 to 20% by weight of the active ingredient. In the case of granules, the active substance content depends in part on whether the active substance is present in a solid or liquid state and on what granulation auxiliaries, fillers, etc. are used.

In addition, the active ingredients, if desired, contain customary adhesives, wetting agents, dispersing agents, emulsifiers, penetration aids, solvents, fillers or carriers. For the purpose of application and on the market, the concentrates are optionally diluted in the customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and, in part, also in the case of microgranules with water. Powder and granular preparations as well as sprayable solutions are usually not further diluted with other inert substances prior to application.

The required application rate varies, inter alia, depending on the external conditions, such as the temperature, humidity below. This amount can vary within wide limits, for example between 0.005 and 10.0 kg / ha or more of active substance, but preferably it is 0.01 to 2 kg of active substance / ha.

If desired, mixtures or admixtures and other active substances are also possible, such as, for example, insectioids, acaricides, herbicides, fertilizers, growth regulators or fungicides.

The following examples illustrate the invention. .

A. Examples illustrating the composition and preparation of compositions

The dust is obtained by mixing 10 parts by weight of active ingredient and 90 parts by weight of talc or inert substance and comminuting the resulting mixture in a hammer mill. A water-dispersible wettable powder is obtained by mixing 25 parts by weight of the active ingredient, 64 parts by weight of quartz containing kaolin as inert substances, 10 parts by weight of potassium ligninsulfonic acid and 1 part by weight of sodium oleoylmethyltaurine as a wetting agent. with a dispersant and the resulting mixture is ground in a pin mill.

A water-dispersible dispersion concentrate is obtained by ee mixing 20 parts by weight of the active ingredient ee 6 by weight of alkylphenol polyglycol ether (Triton X 207), 3 parts by weight of isotridocanol polyglycolother (8 moles of ethylene oxide) and 71 parts by weight of paraffinic mineral oil (boiling range). for example about 255 to 377 ° C) and the resulting mixture is ground in a friction ball mill to a particle size below 5 ytua.

The emulsifiable concentrate was obtained from 15 parts by weight of the active ingredient, 75 parts by weight of the cyclohexanone solvent and 10 parts by weight of the oxethylated nonylphenol (10 moles of ethylene oxide) as an emulsifier.

B. Examples illustrating a process for the manufacture of active ingredients

Example 1

2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-imidazol-1-yl-4,5,6H-tetrahydrolsoindolinone

CS 268 818 B2

1.36 g (20.0 mmol) of imidazole and 2.76 g (20.0 mmol) of potassium carbonate were heated in 40 ml of acetonitrile to 60 ° C. 6.40 g (20.0 pitch) of 3-chloro-2- (4-chloro-2-fluoro-5-aethoxyphenyl) -4,5,6,7-tetrahydreisoindine is then added dropwise at a temperature of 60 ° C. of olinone dissolved in 20 ml of acetonitrile. The reaction mixture was stirred at 60-70 ° C for 4 hours to complete the reaction. The reaction mixture was poured into 250 ml of water and extracted with 10 ml of methylene chloride. The methylene chloride phase is washed again with 100 ml of water and dried over sodium sulfate. After removal of the solvent by distillation, the remaining solid residue is triturated with petroleum ether and then the product is filtered off. 5.6 g (80.0% of teeris) of 2- (4-chloro-2-fluoro-5-methexyphenyl) -3-thiazol-1-yl-4,5,6,7-tetrahydroisoindolinone are obtained in the form of light brown 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 the triazole and 2.76 g (20.0 MAO ^) of potassium carbonate under hříváve 40 ml of acetonitrile at 60 ° C _# at 60 ° C was added dropwise 5.64 g (20 0 mmol)

3-chloro-2- (4-chlorophenyl) -4,5,6,7-tetrahydroisoindolinone dissolved in 20 ml acetonitrile. The reaction mixture was stirred at 70 ° C. until completion of the reaction (5 hours) and then poured into 250 ml of water. Extraction is carried out with 100 .mu.l of methylene chloride, the methylene chloride phase is washed with 100 ml of water and dried over sodium sulfate. After removal of the solvent by distillation, the remaining solid residue is triturated in petroleum ether and then the product is filtered off. 5.40 g (86% of theory) of 2- (4-chlorophenyl) -3- (1,2,4-trlazol-1-yl) -4,5,6,7-tetrahydroiseindolinolinone are obtained in the form of pale yellow m.p. 64-68 ° C. ’

Example 3

2- (4-Chloro-2-fluoro-5-isopropoxyphenyl) -3-diethoxyphosphoryl-4,5,6,7-tetrahydroisoindolinone

17.9 g (0.05 mmol) of 3-chloro-2- (4-chloro-2-fluoro-5-isoproposyphenyl) -4,5,6,7-tetrahydroisoindolinone and 10.0 g (0.06 mmol) triethylphosphite is heated to 70 ° C with 30 ml of potassium iodide. After the gas evolution had ceased, the reaction mixture was heated at 10 ° C for 30 minutes. The reaction mixture, which partially crystallizes on cooling, is heated with 150 ml of ether and then the precipitate is filtered off. 21.0 g (92% of theory) of 2- (4-chloro-2-fluoro-5-isopropoxyphenyl) -3-diethylphosphoryl-4,5,6,7-tetrahydroisoindolinone are obtained in the form of colorless crystals, m.p. Mp 110 ° C.

Example ±

2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-thiocyanato-4,5,6,7-tetrahydroisoinolinone

6.4 g (0.02 mmol) of 3-chloro-2- (4-chloro-2-fluoro-5-methoxyphenyl) -4,5,6,7-tetrahydroisoináolinone and 3.2 g (0.01 mol) lead thiocyanate is heated at 70 ° C in 80 ml toluene for 3 hours. Then the lead chloride formed is filtered off, the toluene phase is washed briefly with 100 ml of water, dried over sodium sulphate and then distilled off by the solvent. The residue was dried under reduced pressure at 40 ° C to constant weight. September ₀ ka ee 6.3 g (92 £) of 2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-thiocyanato-4,5,6,7-tetrahydroisoindolinonu as a viscous yellow oil.

(a) 1 H-NMR spectrum (perdeuterated dimethyl sulfoxide, J-value in ppm):

1.3-2.6 (m, 8H, 1H of cyclohexene ring),

CS 268 818 B2

3.8 ( _β , ЗН, ОСН ₃ ), 6.0 ( _β> 1Н, Н а С-3),

6.9-7.3 (а, 2Н, aromatic Н)

Ь) ektrδ epectrua * vapor at 2020 ca * ¹ (NCS band)

Example 5

2- (2-chloro-4-fluoro-5-methoxyphenyl) -3-pyrrolyl-4,5,6,7-tetrahydroisoindolinone

1.34 g (0.02 mol of pyrrole and 2.0 g (0.02 mol) of triethylamine are dissolved in 40 ml of toluene and 6.4 g (0.02 aol) are added dropwise to the solution at room temperature.

3-chloro-2- (4-chloro-2-fluoro-5-methoxyphenyl) -4,5,6,7-tetrahydroisoindolinone dissolved in 30 mL of toluene. The reaction mixture was stirred at 70 ° C for 3 hours, then twice with 100 ml of water each time and dried over sodium sulfate. After evaporation of the solvent, 6.20 g (89% of theory) of 2- (2-chloro-4-fluoro-5-methoxyphenyl) -3-pyrrolyl-4,5,6,7-tetrahydro-4-indolinene is obtained in the form of a brown oil.

The compounds listed in the following Table 1 can also be prepared in an analogous manner.

Table 1 H. A. 0 example O aaalogíoky number AND R ^ physical data according to

Even ^х * 4-Cl-C ₆ H ₄ 1 68-72 TT

T 4 -Cl-2-F-5-CH (CH 2) 2 * ^c 6 ^H 2 H-NMR spectrum (perdeuterated dimethyl sulfoxide, ppm ppm): 1.1-1.5 (a, 6H, -OCH ( CH ₃ ) ₂ ), 1.5-2.6 (m, 8H, cyclohexene ring H), 4.3 (α, 1H, -OCH (CH ₃ ) ₂ ), 6.6 ( _β , 1H, H at C-3), 6.7 and 7.1 (2d, 2H, aromatic H), 6.9 and 8.2 (2β, 2H, triazole-H) 2

20 May AND 2,4-? 2-С _б Н ₃ 49 0 P (OC ₂ H ₅ ) ₂ 4-Cl-2-P-5-OCH ₃ -C ₆ H ₄ 50 h 4-Cl _4-CGH 53 к 2,4-? ₂ -C ₆ H ₃

@ 1 H-NMR (.delta., Dimethylsulfoxide, ppm): 1.3-2.6 (m, 8H, cyclohexene ring), 6.4 (s, 1H, H on C-3), .delta. Ζ-7.6 (m, 5H, aromatic and imidazole)

H) 1

m.p. 128-131 .3

m.p. 112-1133 yellow oil ’3

СЗ 268 818 В2 cont. Melting of Table 1 Example No. AR ² Physical data analogous to Example 1

$ (OCH _{3) 2}

8J -SCN

2,4-Cl ₂ -5-OCH ₃ -C ₈ H ₂

-3CN 4_Cl_CgH ₄

S7 -SCN 2,4-У ₂ -С _б Н ₃

108 R tOCgH-2,4-Cl ₂ -5-0CH ₃ -C ₆ H ₂

m.p. 119-121 yellow oil

mp 105-107 @ 1 H-NMR (CDCl3): 1.6 (s, 1H, cyclohexenyl), 2.4 (0.4H, cyclehexenyl), 3.8 (s, 3H). OCH 2, 6.2 ( _e , 1H, CHSCN), 7.2-8 _t 6 (α, 3H, aromatic)

m.p. 164-166

109 T

4-Cl-2-K5-0CH ₃ -C ₆ H ₂ ^ H-NMR Spectrum (perdeuterated dimethylsulfoxide hednotycTv ppm)

1.5-2.6 (m, 8H, cyclohexenyl, 3.9 (0, 3H, OCH ₃ ), 6.6 (0, 1H, CH-triazole), 6.7 and 7.1 (2d, 2H) , aromatic),

7.9 and 8.1 (2s, 2H, triazole)

114

125 £ (OCH ₃ ) ₂ 2,4-Cl ₂ -5-CO ₂ C ₂ H ₅ -C ₆ H ₂

m.p. 119-122

m.p. 121-125

Explanatory notes to Table 1 *

Example 129

[2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-oxo-2,3,4,5,6,7-hexahydre-1H-ioindol-1-yl] phosphonate monoethyl

8.6 g (20 mmol) of 2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-diethoxyphosphoryl-4,5,6,7-tetrahydroisoindolinone (Example 49) is stirred vigorously for 4 hours at a temperature of 100 ° C in 80 ml of 10% hydrochloric acid. Aqueous hydrochloric acid is then removed at 50 ° C under a water pump vacuum. The resin residue is resuspended in 100 ml of 5% potassium hydroxide solution and the solution is extracted with 50 ml of ethyl acetate.

CS 268 818 B2

The aqueous phase is acidified to pH 2 with concentrated hydrochloric acid under ice-cooling and the precipitate formed is filtered off and dried. 6.2 g (77% of theory) of monoethyl-2- (4-chloro-2-fluoro-5-aethoxyphenyl) -3-oxo-2,3,4,5,6,7-hexahydro-1H-ideindole are obtained. 124 DEG-126 DEG C. The title compound is obtained in the form of colorless crystals.

Example 130

Monoethyl T2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-oxo-2,3,4,5,6,7-hexahydro-1H-1H-indol-1-yl] phenylacetate potassium salt

8.5 g (20 mmol) of monoethyl 2- (4-chloro-2-fluoro-5-methoxyphenyl) _-3-oxo-2-f 3,4,5,6,7hexahydro ieoindol-lH-yl foefonátu (Example 129) and 1.12 g (20 mmol) of potassium hydroxide are stirred in 100 ml of methanol at 20 DEG C. for 30 minutes. The solvent was evaporated and the residue was dried. 9.4 g (100% of theory) of the monoethyl-C2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-oxo-2,3,4,5,6,7-hexahydro potassium salt are obtained. 1 H-isoindol-1-yl] phi-phonate in the form of pale yellow crystals melting at 151-153 ° C with decomposition.

Example 131

2- (4-chlorophenyl) -3-oxo-2.3 _t 4,5,6,7-hexahydro-isoindole-l-acid yl3fOBfonová

19.2 g (0.05 mol) of 2- (4-chlorophenyl) -3-diethoxyphosphoryl-4,5,6,7-tetrahydroisoindolinone (Example 50) is stirred for 2 hours in 130 ml of concentrated hydrobromic acid at 100 ° C. then the reaction mixture is rotary evaporated and the residue is dried at 50 ° C under high vacuum. Zíeká 16.1 g (98%) £ 2- (4-Chlorophenyl) -3-oxo-2,3,4,5 _t 6,7-hexahydro-lH-isoindol-l-ylJfosfenové acid as colorless crystals mp 103-106 ° C.

Example 1 a d 132

C 2- (4-Chlorophenyl) -3-oxo-2,3,4,5,6,7-hexahydro-1H-isoindol-1-yl] phosphonic acid dibasic salt

16.4 g (0.05 mol) of C2- (4-chlorophenyl) -3-oxo-2,3,4,5, n-hexahydro-1H-isoindol-4-yl-4-oxoic acid (Example 131) ) and 5.6 g (0.10 mol) of potassium potassium hydroxide are dissolved in 200 ml of methanol and the reaction solution is stirred for 30 minutes at 20 ° C. The methanol is now distilled off and the residue is dried. 22.0 g (100% of theory) of the 2- (4-chlorophenyl-3-oxo-2,3,4,5,6,7-hexahydro-1H-isoindol-1-yl) phosphonic acid dipotassium salt are obtained in the form of yellow salts. crystals melting with decomposition at 188 to 190 ° C,

Example 1 a d 133

£ Ethyl 2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-oxo-2 _f 3,4,5,6,7-hexahydro-i _B-L-oindol yljmethylfosfinát

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 methanephosphoric acid ester was heated together with 10 mg of potassium iodide for 20 minutes at 120 ° C. The solid obtained is boiled with 100 ml of ether and then the reaction mixture is filtered. It is obtained

11.4 g (95% of theory) of ethyl E2- (4-chloro-2-fluoro-5-aethoxyphenyl) -3-oxo-2,3,4,5,6,7-hexahydro-1H-ioindole-1 m.p. 180-183 ° C.

Example 134

C2- (4-chloro-2-fluoro-5-mothoxyphenyl) -3-oxo-2,3,4,5,6,7-hexahydro-1H-isoindol-1-ylmethylphosphinic acid

CS 268 818 B2

12.1 g (0.03 mol) of ethyl 2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-oxo-2,3,4 _t 5,6,7-hexahydro-l-lselndel The methyl methylphosphinate (Example 133) was stirred in 120 ml of 20% hydrochloric acid at 100 ° C and then the reaction mixture was rotary evaporated. The residual resin was dissolved in 100 ml of 10% potassium hydroxide solution and the solution was extracted with 50 ml of ethyl acetate. The aqueous phase ee is adjusted to pH 2 by adding concentrated hydrochloric acid under ice-cooling, and the precipitate formed is filtered off and dried. 10.4 g (93% of theory) of 2- (4-chloro-2-fluoro-5-methexyphenyl) -3-oxo-2,3,4,5,6,7-hexahydro-1H-isolndole-1 are obtained. 153-155 ° C; methyl methylphosphine cyeelines in the form of colorless crystals;

• 'Example 1 a d 135

2- (4-Chler-2-fluoro-5-methoxyphenyl) -3-exo-2,3,4,5,6,7-hexahydro-1H-isoindel-1-yl methylphosphine acid potassium salt

7.5 g (0.02 mol) 2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-oxo-2,3,4,5,6,7-hexahydro-1H-isoindole-1- of methyl methylphosphinic acid (Example 134) and 1.12 g (0.02 mol) of potassium hydroxide are dissolved in 100 ml of methanol and the methanolic solution is stirred for 20 minutes at 20 ° C, then the solvent is evaporated and the residue dried at 50 ° C under high vacuum. 8.3 g (100% of theory) of potassium aoli are obtained

2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-oxo-2,3,4,5,6,7-hexahydro-1H-isolndol-1-yl methylphosphinic acid in the form of pale yellow crystals which melting with decomposition at a temperature of ГМ to 177 ° C.

Example 136

2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-diphenylphosphinyl-4,5,6,7-tetrahydroisoindolinone

9.9 g (0.03 mol) of 3-chloro-2- (4-chloro-2-fluoro-5-methoxyphenyl) -4,5,6,7-tetrahydroisoindolinone and 6.9 g (0.03 mol) Ethyl diphenylphosphonate was heated to 120 ° C with 20 mg of potassium iodide for 30 minutes. The remaining 2-residue was boiled with 150 ml of ether and the product was filtered off. 13.4 g (90% of theory) of 2- (4-chloro-2-fluoro-5-methoxyphenyl) -3-diphenylphosphoryl-4,5,6,7-tetrahydroisoindolinolinone are obtained in the form of colorless crystals of melting point 207 to 209

In an analogous manner to that described in the above examples, the compounds shown in Table 1 below are also obtained.

continued Table 1 example analogously to

No. AND R ² physical data example 139 J (OC ₂ H ₅ ) ₂ 4-Br-C ₆ H ₄ m.p. 128-131 3 140 í (O 2) 2 4_J_CgH ₄ m.p. 150-153 3 141 - | - ^OC 5 OH 4_J_C _g H ₄ m.p. 126-128 129 14 2 Л-ОК ÓCjHj 4-Cl _4-CGH m.p. 151-153 130 143 J (OH) ₂ 4-Br-C ₈ H ₄ t.r. 143-145 131 167 4-Br-3-CO ₂ C ₃ H ₇ -C ₈ H ₃ @ 1 H NMR (deuterochlo-

roform or perdeuterated dimethylsulfoxide, ppm ppm): 0.9-1.5 (m, 12H, CO ₂ CH (CH ₃ ) ₂ and PO (CCH ₂ CH ₃ ) ₂ ), 1.2-2.7 (а, 8H,

CS 268 818 B2 continued Table 1

cyclohexenyl), 3.5-4.3 (α, 4H, δ (OCH ₂ CH ₃ ) ₂ ), 4.9 (d, 1H, CH-PO), 5.1 (m, 1H, CO ₂ CH ( CH ₃ ) ₂ ), 7.3-7.9 (», 3H, aromatic) 3 144 LoC ^ 4-Cl _4-CGH 133 177 p (oc ₄ H ₉ ) ₂ 4-Cl-3-CO ₂ C ₂ H ₅ -C ₆ H ₃ ¹H-NMR (CDCl or perdeuterated dimethylsulfoxide hodnotycTv ppm): 0.7 to 2.8 (m, 25H), 3.4-4.1 (m, 4H, _CH2), 4.3 (d, 2H, CO ₂ CH ₂ CH ₃ ), 3.9 (d, 1H, CH-PO, 16Hz), 7.3-8.0 (α, 3H, aromatic) 3 180 0 1 (00 ^ 5) 2 0 4-Cl-3 CCO ₂ CH _{(CH3) 2C2 H5} CO 3 -C ₆ ^H 3 NMR (CDCl or perdeuterated dimethylsulfoxide hodnotycfv ppm): 0.9 to 2.8 (m, 20H), 3.6 to 4.5 (m, 6H, CH ₂ P (O) - (OCH ₂ CH _{3) 2,} 5.1 (d, 1H, CH-PO _r J «16 Hz) y 5.3 (q, 1H, CO ₂ CH (CH _{3) 2,} 7.3 to 8.1 (m, 3H, aromatic ) 3 204 ^ (00 ^ 5) 2 0 4-С1-2Р-5- (0СН ₂ С _и С) _ “ ^C 6 ^H 2 m.p. 124-127 3 205 8 (00 ^ 5) 4-Вг-2Р-5-ОСЯ ₃ -С ₆ Н ₂ tet · 146 3

C. Examples illustrating biological activity

Weed damage or crop tolerance is assessed on a scale in which the efficacy is expressed as 0-5.

It means:

. without effect or damage

0 to 20% effect or damage 20 20 to 40% effect or damage

- 40 to 60% effect or damage «60 to 80% effect or damage« 80 to 100% effect or damage

1. Effect on weeds in pre-emergence treatment

Seeds or pieces of rhizomes of monocotyledonous and dicotyledonous weeds are placed in plastic pots (9 cm diameter) with baking-clay soil and covered with a layer of soil. The compounds of the invention formulated as wettable powders or emulsion concentrates are then applied in the form of aqueous suspensions or emulsions with an amount of water of 600 liters / ha in varying amounts on the surface of the soil forming the covering layer. After treatment, the pots are placed in a greenhouse and maintained under good growth conditions for weeds (temperature: 23 ° C + 1 ° C, relative humidity 60 to 8 ° C).

CS 268 818 B2

Visual assessment of plant damage or emergence damage is performed after emergence of the test plants for 3-4 weeks as compared to the untreated control.

The values of this evaluation shown in Table 2 show that the compounds of the invention have good herbicidal activity in pre-emergence treatment against a wide range of monocotyledonous and dicotyledonous weeds.

Table 2

The herbicidal effect of the compounds according to the invention in pre-emergence treatment Example compound rate (kg / ha) SIA herbicidal effect CRS QUARRY ECG 5 2.5 5 5 5 5 49 2.4 5 5 5 5 0.6 5 5 5 5 0.15 * 4 1 2 50 2.5 3 4 5 5 3 2.4 5 5 5 5 0.6 5 5 5 5 0.15 1 2 1 1 6 2.5 4 5 5 4 2 2.5 3 4 5 5 1 2.4 5 5 5 5 0.6 5 5 5 5 0.15 2 2 1 1 8 2.5 5 5 5 5 53 2.5 4 5 5 5 4 2.4 5 5 5 5 0.6 5 4 5 5 0.15 2 1 3 1 20 May 2.5 4 5 4 4 67 2.5 2 5 5 4 85 2.5 3 5 5 5 87 2.4 5 5 5 5 0.6 2 5 4 4 0.15 2 2 2 2 108 2.5 5 5 5 4 109 2.4 5 5 5 5 0.6 5 5 4 5 0.15 2 3 2 2 114 2.5 4 5 5 5 125 2.5 3 5 4 3 129 2, Ί 5 5 5 5 0.6 3 4 5 4

CS 268 818 B2

Example compound dose (kg / ha) SIA herbicidal effect CRS QUARRY ECG 0.15 2 2 1 1 8 2.5 5 5 5 5 53 2.5 4 5 5 5 4 ² . ⁴ 5 5 5 5 0.6 5 4 5 5 0.15 2 1 3 1 20 May 2.5 4 5 4 ’4 67 2.5 2 5 5 4 85 2.5 3 5 5 5 87 2.4 5 • 5 5 5 0.6 2 5 4 4 ... 0.15 2 2 2 2 108 2.5 5 5 5 4 109 2.4 5 5 5 5 0.6 5 5 4 5 0.15 2 3 2 2 114 2.5 4 5 5 5 125 2.5 3 5 4 3 129 2.4 5 5 5 C ✓ o, 6 3 4 5 4 0.15 2 3 3 2 131 2.5 5 5 3 5 132 2.5 2 3 5 3 133 2Л 5 5 5 5 0.6 5 5 5 5 0J15 4 5 5 5 134 2.4 5 5 5 5 0.6 3 4 5 5 0.15 1 2 3 1 136 2.4 5 5 5 5 0.6 5 5 5 5 0.15 2 3 4 1 139 2.4 5 5 5 5 0.6 2 3 5 4 0.15 1 1 3 1 140 2.5 1 1 5 1 142 2.5 4 5 4 5 143 2.5 2 3 5 5

en 268 818 B2

Example compound dose (kg / ha) SIA herbicidal effect CRS QUARRY ECG 144 2.5 5 5 5 5 204 2.4 5 5 5 5 0.6 5 5 5 5 0.15 4 5 5 3 205 ² ' ⁴ 5 5 5 ^: 5 0.6 5 5 5 5 ' 0.15. 4 4 4 3 167 2,4 ' 3 5 5 5 0.6 2 5 4 4 0.15 2 5 2 1

Abbreviations:

SIA = Field Mustard (Sinapis arveneis)

CRS c Daisy (Crysanthemum segetum) LOM = Ryegrass (Lolium multiflorum) ECG _c Echinochloa crue galii

2. Effect on weeds in post-emergence treatment

Seeds or pieces of rhizomes of monocotyledonous and dicotyledonous weeds are placed in plastic pots (9 cm in diameter) in sand-clay soil and covered with a layer of soil and grown in a greenhouse under good growth conditions. Three weeks after sowing, the test plants are treated at the three leaf stage. The compounds according to the invention, processed as wettable powders or as emulsion concentrates, are applied in various doses to the green parts of the plants using water in an amount of 600 liters per hectare and after about 3-4 weeks of storage of the test plants in water. greenhouse under optimal growth conditions (temperature: 23 ° C ♦ 1 ° C, relative air humidity 60 to 80%) visually evaluate the effect of the preparations in comparison to untreated control.

The compositions according to the invention have good herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous weeds even after the post-emergence treatment (cf. Table 3).

Table 3

The herbicidal effect of the compounds according to the invention in the post-emergence treatment

Example compound dose (kg / ha) SIA herbicidal CRS effect QUARRY £ CG 5 2.5 '4 3 4 2 49 2.4 5 5 5 5 0.6 4 4 2 1 0.15 1 3 2 2 3 2.4 5 5 5 4 0.6 i T 5 4 3 0.15 2 4 2 2 1 2.4 5 5 3 3

CS 268 818 B2

compound dose herbicidal effect from the example (kg / ha) SIA CRS QUARRY ECG

0.6 0.15 5 2 3 2 2 1 3 2 8 2.5 4 4 3 3 4 2.4 5 5 5 5 0.6 5 5 3 4 0.15 4 3 2 2 67 2.5 3 4 1 2 87 2.4 5 5 4 4 0.6 4 4 3 1 0.15 1 1 1. 1 109 2.4 5 5 5 5 o, 6 3 3 3 4 0.15 2 3 2 3 114 2.5 4 3 4 2 125 2.5 5 5 1 2 129 2.4 5 5 5 5 0.6 4 4 3 3 0.15 2 2 1 1 133 2.4 5 5 5 5 0.6 5 4 4 5 0.15 3 2 2 2 134 2.4 5 5 5 5 0.6 5 4 3 4 . 0.15 2 3 1 2 131 2.5 5 2 5 4 132 2.5 5 2 5 2 136 2.4 5 5 5 5 0.6 5 4 4 3 0.15 4 2 2 1 139 2.4 3 3 4 5 0.6 3 2 3 3 0.15 1 1 1 1 142 2.5 • 5. 1 4 1 143 2.5 5 1 5 2 144 2.5 4 1 5 2 204 2.4 5 5 5 5 0.6 5 5 5 4 0.15 5 5 4 2 205 2.4 5 5 5 5 0.6 5 4 4 5

Example compound rate (kg / ha) Slá herbicidal effect CRS QUARRY • ECG 0.15 4 4 3 2 167 2.4 5 5 2 4 0.6 5 5 2 4 0.15 3 4 1 2 177 2.4 5 5 5. 5 * 0.6 4 5 3 4 0.15 1 3 2 • 2 180 2.4 5 5 3 5 0.6 4 5 2 3 0.15 2 5 1 1

Abbreviations: егоv. Table 2

3 »Tolerance of crop plants

In further greenhouse experiments, seeds of a plurality of crops are placed in pots filled with sand-clay soil and covered with a layer of soil. A portion of the pots were treated immediately as described in FIG. 1. The remaining pots are placed in the greenhouse until two or three true leaves have been developed and then sprayed with the compounds of the invention at different dosages as described in Section 2.

Four to five weeks after application and storage in the greenhouse, a visual assessment is made to ensure that the compounds of the invention leave dicotyledonous crops such as soybean, bavaria, rape, sugar beet and potatoes undamaged even during pre-emergence and post-emergence treatment at high doses. In addition, some of the compounds of the invention also tolerate monocotyledonous crop plants, such as barley, sorghum, maize, wheat or rice. Thus, the compounds of formula I have a high selectivity when used to combat undesirable plant growth in agriculturally important crops.

Claims (3)

SUBJECT OF THE INVENTION Herbicidal composition, characterized in that it contains, as an active ingredient, at least one compound of the general formula I (I) in which: R ² is 4-chlorophenyl, 4-bromfenyloveu group, 4-iodophenyl, 2,4-difluorophenyl, 2,4-dichloro-5-methexyfenylovou group, 4-chloro-2-fluoro-5-methoxyphenyl, 4-bromo-2-fluoro-5-methexyphenyl, 2,4-dichloro-5-ethoxycarbonylphenyl, 4-chloro-3-ethoxycarbonylphenyl, 4-chloro- 2-fluoro-5-isopropoxyphenyl, CS 268 818 B2 4-bromo-3- (propoxycarbonyl) phenyl, 4-chler-2-fluoro-5 _T propargylexyfenylovou, 4-chler-2-fluoro-5- (l-ethoxycarbonylethoxy) fenyloveu sky group of 4-chloro-2-fluoro -3- (1-ethoxycarbonylethoxy) phenyl and represents imidazol-1-yl, 1,2,4-triazol-1-yl, thiocyanato, pyrrolyl R ⁹ or a group R ¹⁰ where R ⁹ and R ¹⁰ are each independently hydroxy, -OK, methyl, phenyl or butoxy. methoxy, ethoxy, hy2. 2. A composition according to claim 1, wherein the active ingredient comprises at least one compound of formula (I) in which: R ² is 4-chlorophenyl, 2,4-difluorophenyl, 2,4-dichloro-5-methoxyfenyloveu group, 4-chloro-2-fluoro-5-methoxyphenyl group, the 2,4-dichloro-5-ethoxykarbonylfenylovou group, 4-chloro-3-ethoxycarbonylphenyl, 4-chloro-2-fluoro-5-isopropoxyphenyl or 4-chloro-2-fluoro-5- (1-ethoxycarbonylethoxy) phenyl and is imidazol-1-yl, 1, 2,4-triazol-1-yl, thiocyanato, pyrrolyl or a group of formula> 9 R ¹⁰ where r ⁹ _λ ηΐθ are, independently of each other, a methoxy group or an ethoxy group. 3. A composition according to claim 1, wherein the active ingredient comprises at least one compound of formula (I) wherein: R ² represents a group means 4-chlorophenyl, 4-bromophenyl, 4-jedphenyl or 4-chloro-2-fluoro-5-methoxyphenyl and a group of the formula R ⁹ where R ⁹ and R ¹⁰ independently of one another represent a hydroxyl group -OK, ethoxy, methyl or phenyl. 4. A process for the preparation of an active compound according to claim 1, which process comprises treating a compound of the formula II R ¹² (II) in which R ² R ¹² will CS 268 818 B2 has the meaning given in the meaning of the nucleofugyl group, point 1 and a group such as a halogen atom, a tosyl group or a meso-introducing residue H-A, M-SCN A of the general formula or R R *O-P · wherein AND* R ¹ R ⁹ se R ² R ¹² has the meaning of A, said metal cation, preferably a cation, is an alkyl group having 1 R ¹⁰ are as defined in point 1. by acting R ^{9 R10} bodJ 1 except the group -P (0) (R ⁹⁾ (R ¹⁰⁾ and -NCS, lead cation, potassium cation or sodium up to 4 carbon atoms and 5. A process for the preparation of an active ingredient that ев to a compound according to the general formula II, ve 2, wherein the formula I is as defined for the compound wherein: AND* R ¹ R ⁹ and R ¹⁰ R ² R ¹² acts as mentioned in 2 and 4 misleading the residue Η - λ 'M - SCN has the meaning of symbol A, which and NCS, A of the general formula or R ^O-P is a metal cation, preferably a cation, represents an alkyl group having 1 as defined in point 2. R ⁹ R ^{10 is} given in point 2 except for the group -P (O) (R ⁹ ) (lead cation, potassium cation or sodium up to 4 carbon atoms and according to point II), 6. A process for the manufacture of an active ingredient that has the meaning given to a compound as defined by a compound misleading in which ve 3, of formula (I), characterized in that point 2 and point (4), residue A of formula (I) R ¹ OP R ⁹ R ¹⁰ R ¹ represents an alkyl group having 1 to 4 carbon atoms and R ⁹ and as defined in point 3.