DD264844A5 - HERBICIDE MEDIUM - Google Patents

Abstract

The invention relates to herbicidal compositions which, as active ingredient, are compounds of the formula (I) or salts thereof in which Ar, R 1, R 2, R 3, M, Q, T, X and Y have the meaning given in the description, in addition to customary auxiliaries. and Traegerstoffen, included. They have excellent herbicidal activity and are particularly suitable for use in agriculture. Formula (I)

Description

Herbicidal agents Field of application of the invention

The present invention relates to herbicidal agents and is therefore used in agriculture for controlling undesirable plants in crops.

Characteristic of the known state of the art

Blycellic imides with herbicidal activity are described in EP-A 70 389, EP-A 104 532 and US Pat. No. 4,179,276.

Surprisingly, new bicyclic imides have now been found "which have significantly better herbicidal activity with excellent selectivity."

aim the invention

Oils of the invention have excellent herbicidal activity against a wide range of important mono- and dikotyler weeds in wheat barley, rye, rice, maize, sugar beet, cotton, soy and. a. Crops on crops, without the crops are damaged in any appreciable way.

Explanation of the essence of the invention

The invention has for its object to provide herbicidal agents available.

- la -

The present invention relates to herbicidal compositions containing as active ingredient compounds of the formula I or salts thereof,

R _n R. "

Ar is phenyl, naphthol, pyridyl, quinolinyl or isoohinolinyl, where these radicals are one to four times, preferably one to three, identical or different radicals of the group halogen, hydroxy, (C.-C.) alkyl, halo ( C ₁ -C ₄ ) SlICyl, (C ₁ -C ₄ ) alkoxy, (C ₃ -C ₆ ) CyClOlkoxy, (C ₃ -C ₆ ) alkenyloxy, (C ₃ -C ₆ ) alkynyloxy, (C ₁ -C ₄ ) Alkenoxy (C ₁ -C ₄ ) alkoxy, halo (C ₁ -C ₄₎ 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 ₄ ) alkylsulfonyl, NO ₂ , »CN, -NHR ₁ , CyBnO (C ₁ -C ₄ alkyl, phenoxy, phenoxy-C ₁ -C ₄ -alkyl, Phenyl (C ₁ -C ₄ ) alkoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, where the six last-mentioned radicals in the phenyl ring are formed in trisubstituted by halogen, (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ ) -alkoxy, (C ₁ -C ₄ ) -

Alkoxycarbonyl, -CN or NO 2 may be substituted, or further by a radical of the formulas

-JZR ₄ , -OP (XR ₅ ) ₂ or

may be substituted;

Ri is hydrogen, (Ci ~ _C4) alkyl or phenyl which is substituted up to two times by halogen, (Ci-C ₄₎ alkyl, (Ci-C ₄₎ alkoxy, NO ₂ I CN or (Ci-C ₄₎ alkoxycarbonyl can be,

R2 »Rj is independently hydrogen, (Ci-C ₄₎ alkyl which may be substituted by cyano, hydroxy or (C ~ _C4) alkoxy, phenyl or benzyl, both in the phenyl ring in each case preferably up to 2 times by halogen, (C 1 -C ₄ ) alkyl, (C 1 -C ₄ ) Al! Oxy, NO ₂ or -CN may be substituted; (C 1 -C ₄ ) alkoxy, (C 1 -C ₄ ) Al'KOxycarbonyl, halideC ₄ ) alkoxycarbonyl, (C 1 -C ₄ ) -alkoxy (C 1 -C ₄ ) -alkoxycarbonyl, (C 1 -C ₄ ) -alkoxycarbonyl (Ci C ₄ ) alkoxycarbonyl, carboxy, or a residue of the formulas

Pi / ^R 11 ^R 1 / ^R 10

-C-N-N, -C = N-N or

O ^X Rio ^N Rii

X

RV Λ

R ₄ is hydrogen, (Ci-C ₄₎ alkyl, up to six times by halogen and / or up to disubstituted by (Ci-C ₄₎ alkoxy, (Ci-C ₄₎ alkoxy (Ci-C ₄₎ alkoxy, (C Alkoxycarbonyl, (C ₁ -C ₄ ) alkylthio, (C ₁ -C ₄ ) alkyl

Bulfinyl, (C 1 -C ₄ ) alkylsulfonyl, (C 1 -C ₄ ) -alkylamino,

-CN, furyl, tetrahydrofuryl, benzofuryl, phenyl, phenoxy, benzyloxy, where in the six last-mentioned radicals, the phenyl ring or the heteroaromatic may be substituted in each case up to three times by halogen, (C 1 -C 4) -alkyl or (C 1 -C 4) -alkoxy, (C ₁ -C 5) -cycloalkyl, (C ₁ -C 6 -alkenyl, cyclohexenyl, (C ₁ -C 8) -alkynyl, phenyl which may be substituted up to three times by halogen, (C ₁ -C 4) -alkyl, (C ₁ -C 4) -alkoxy or (C ₁ -C 4) Alkoxycarbonyl or a radical of the formula

-N = C

the latter remainder being excluded for Z = S

Rtj Wanserstofi or (C ₁ -C 4) Aikyl _/

R6 is hydrogen, (C ₁ -C 4) alkyl or together with R 4 and the nitrogen atom connecting these radicals a 5- to 7-membered heterocycle containing as ring members one or two radicals of the group -O-, -S-, -NR 5 - and may be up to 3 times substituted by (C 1 -C 4) alkyl;

R7 is hydrogen, (Ci-C4) alkyl, phenyl or benzyl, wherein the phenyl ring may be substituted in each case up to three times by halogen, (Ci-C4) alkyl, (Ci-C4) A1-koxy, (C ₁ -C4) alkoxycarbonyl , -NO 2 »CF 3, -CN or a residue of the formulas

-JN, -C-OR ₁ , -CR ₁ , -P (XRj) ₂ or

X ^X Re Ö 0 X

-SR ₁ , 11.

(O) n

R8 » ^R 9 ^{unat> n} are hydrogen or hydrogen

Alkyl or both Rβ, Rg together with the nitrogen atom connecting them a 5- to 7-membered heterocyclic, which may contain as ring members one or two radicals of the group -0-, -S-, -NR5- and up to three times by (C 1 -C 4) -alkyl, hydroxy, (C 1 -C 4) -alkoxy, phenyl or benzyl, both in the phenyl ring, preferably up to three times, by (C 1 -C 4) -alkyl, (C 1 -C 4) -alkoxy, halogen or (C 1 -C 4) -alkoxy, C4) alkoxycarbonyl may be substituted,

R1O » ^R11 independently of one another hydrogen, (Ci-C4) alkyl,

Phenyl or benzyl, which may each be substituted in each case in the phenyl ring, preferably up to three times, by halogen, (C 1 -C 4) -alkyl, (C 1 -C 4) -alkoxy, NO 2, -CN, CF 3 or (C 1 -C 4) -alkoxycarbonyl, or R ₁ Q and R ^ together the rest

^ R ₁₂

^R 12 » ^R 13 independently of one another, (C 1 -C 4) -alkyl, (C 1 -C 4) -alkoxycarbonyl, phenyl or benzyl, which may both be substituted in the phenyl ring, preferably up to three times, by halogen, (C 1 -C 4) -alkyl , (C 1 -C 4) alkoxy, (C 1 -C 4) alkoxycarbonyl, CP 3, -CN or NO ₂ , 30

^ ? 9 R ₃ Ö

/ R ₂

Q ^e C, -S- or -0-

/ C, -S-, -S-, -S- or -O-,

Ni ₉ 4

X = O or S

Y «0, S or NH,

Z ^ 0, S or NRg,

m = 1, 2, 3 and

η «1 or 2, with the wetness, that if Y« = ο / R ₁ , R ₂ /

R «Η and Q, T β CH, N not CH, 3 2 2

S, SO or SO may be. 2

The compounds of the formula I can be present as pure stereoisomers or their odors. All of these isomeric forms have been covered by the invention.

The salt formation in the compounds of the formula Z can be carried out if R ₂ is R ₃ »carboxy or if ZR ₄ « is OH or SH. Suitable salts are generally those which can be used in agriculture. These include, for example, the alkali metal, alkaline earth metal salts in particular Na, K, Mg, Ca salts, or the salts with ammonium, since one to four times by organic radicals, in particular alkyl or hydroxyalkyl radicals may be substituted.

In the definition of formula I, haloalkyl, haloalkoxy, haloalkenyloxy or haloalkynyloxy contains one or more halogen atoms predominantly one to six F, Cl or Br atoms. These include, for example, the radicals -CF ₃ , -C ₂ F ₅ , -CH ₂ CF ₃ , -CF ₂ Cl, -CF ₂ CHF ₂ , -CF ₂ CHFCl,

-CF ₂ -CH ₂ -CP ₅ , -CF ₂ -CHFBr ₁ -OCF ₅ , -OCF ₂ -CHF ₂ , -OCF ₂ -CHFCl, -OCF ₂ -CHCl ₂ , -CCF ₂ -CHFBr, -OCF ₂ - CHF-CF ₅

Suitable heterocyclic radicals for the grouping Rg-NR ₄ or Rβ-N-Rg are in particular piperidine, pyrrolidine, moipholin or 2,6-dimethylmorpholine.

Preferred compounds of the formula I are those compounds in which 10

Ar = phenyl which may be substituted up to three times by fluorine, chlorine or bromine, (C ₁ -C ₄ ) AlKyI, (C ₁ -C ₄ ) -alkoxy, (C ₃ -C ₄ ) alkenyloxy, (C ₃ - C ₄ ) alkynyloxy _/ halo (C ₁ -C ₄ ) alkyl, halo (C ₁ -C ₄ ) -alkoxy, -NHR ₁ , (C ₁ -C ₄ ) -alkylthio, (C ₁ -C ₄ ) -alkylsulfonyl, NO ₂ or a remainder of the formulas

/ R ₅ \ X -CZR ₄ or -XJ-CACZR _{4 (}

X \ R ₅ / m

R ₁ = hydrogen, (Ci-C ₄₎ -alkyl, (C ^ -C ₄₎ alkoxycarbonyl, R _2, R ₅ * is independently hydrogen, (C ^ -C ₄₎ alkyl, (C ₁ -C ₄₎ alkoxycarbonyl, ( C ₁ -C ₄₎ alkoxy (C ^ -C ₄₎ alkoxycarbonyl, halo (Ci-C ₄₎ alkoxycarbonyl, (C ^ -C ₄₎ alkoxycarbonyl (C ^ -C ₄₎ alkoxyca ^ carbonyl, -CN, carboxy,

-C-N.

0 R9 30

R ₄ = (C ₁ -C ₄ ) Alk ₁ Vl, halo (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxyalkyl, (C ₁ -C ₄ ) alkoxycarbonyl (C ₁ -C ₄ ) alkyl ;

R = H or (C ₁ -C ₄ ) alkyl, R7 = hydrogen, (C ₁ -C ₄ ) alkyl, -CN

Phenyl or benzyl, both of which may be substituted up to two times by (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, halogen, NO ₂ or -CF ₃ ,

R, R = hydrogen, (C ₁ -C ₄ ) alkyl, together with them

connecting N atom of a 6-membered saturated heterocycle

M = C, -O- or -NR ₇ -

η - • '\ W - \ / C or -S T = O or S, X = O or NH, Y = O or S and 2 = 1 mean. m =

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

Ar = phenyl, which may be substituted up to three times by fluorine, chlorine, bromine, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, halo (C ₁ -C ₄ ) BOXOXY, (C ₃ C ₄ ) alkenyloxy, (C ₃ -C ₄ ) alkynyloxy or (C 1 -C ₄ ) alkylthio,

R ₁ = hydrogen or (C ₁ -C ₄ ) AlKyl,

R ₂ , R ₃ independently of one another are hydrogen or (C ₁ -C ₄ ) -alkyl,

- 7a -

M => CR ₂ R ₃ or oxygen, Q / T => CR ₂ R ₃ and 5 X, Y = oxygen.

Another object of the invention are processes for the preparation of compounds of formula (Z) or their salts, characterized in that

a) for Y * O, S is a compound of the formula II with a compound of the formula III,

HN Ar-N = C = X * ^N V-Q ^{/ (III)}

wherein R ^ is H or (C-C) alkyl, or

1

b) reacting a compound of the formula II with an amine of the formula IV

IV

or

c) for Y = O, a compound of the formula X obtained under b) is hydrolyzed and the compounds obtained are optionally converted into their salts.

In process variant a), the reaction for R alkyl is carried out in an inert organic solvent, for example an aromatic solvent such as toluene. Chlorobenzene, a halogenated hydrocarbon such as chloroform, an ether such as di-isopropyl ether or in dimethylformamide, optionally with base catalysis at temperatures of 20 to 12O ⁰ C, preferably 60 to 100 ⁰ C. As bases are preferably organic bases, for example, organic amines such as triethylamine or Pyridine used.

The reaction for R "hydrogen can also be carried out in water as solvent or preferably in the 2-phase system water / organic solvent. Particular preference is given to the procedure in which the compound of formula IXI with an inorganic base, for example an alkali or alkaline earth metal hydroxide, carbonate or hydrogencarbonate such as sodium hydroxide or potassium carbonate, or an organic base such as an organic amine such as triethylamine in the anion is transferred.

To the solution of the anion in water is then the isocyanate or Xsothiocyanat of formula XX, dissolved in a

inert organic solvents such as e.g. Toluene, chlorobenzene, chloroform added dropwise with vigorous stirring.

The aqueous phase is then adjusted with an acid, preferably with a mineral acid such as hydrochloric acid or sulfuric acid to a pH value between 1 and 3 and then further reacted at temperatures between 50 and 100 * C.

In process variant b), the reaction is carried out in an inert organic solvent, for example an aromatic solvent such as toluene, chlorobenzene, a halogenated hydrocarbon such as chloroform or in dimethylformamide at temperatures of 20 to 120 ° C., preferably 60 to 100 ° C.

The hydrolysis according to process variant c) is carried out in water, aqueous mineral acid optionally in the presence of an inert organic solvent at temperatures between 20 and 120 ° C., preferably 60 and 100 ° C. As organic solvents, for example, water-immiscible solvents such as aromatic solvents (e.g., toluene, chlorobenzene) or halogenated ones are used

Hydrocarbons (e.g., chloroform) are contemplated.

The compounds of formula (II) are known or can be prepared analogously to known processes, s. Houben-Weyl, Methods of Organic Chemistry, Vol. VIII, p. 120 (1952), Houben-Weyl Bd IX, p. 875, 869 (1955).

Amines of the formula III are known in part. They can be obtained for Q, M, T CR ₂ R ₅ and Q, T = CR ₃ R ₅ and M * NR ₇ by simple catalytic hydrogenation of the corresponding pyridine or pyrazine derivatives. Amines of the For-

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Del III may also be prepared from amines of formula IV by conversion of the nitrile group by conventional methods, e.g. Org. Synth. Coll. Vol. I, p. 321 (1941) or Houben-Weyl Vol. VIII, p. 536. 5

Amines of general formula IV are known in some cases according to JP-A 3073-569 or can be prepared in an analogous manner by the process described therein.

The erfindungegemäßen compounds of formula I have

an 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 the pre-sowing, pre-emergence or post-emergence process.

For example, the following harmful plants can be combated: grass weeds such as Avena fatua, Alopeus ep *, LoIium sp., Setaria sp., Digitara bp., Sorghum halepense Echinochloa ep., Agropyron ep., Cynodon bp., Fhalaris sp., Dicotyledonous plants such as Lamium ep., Veronioa ep. Galium ep., Stellaria sp., Natricaria sp., Papaver ep., Centauria sp., Amaranthus ep., Galineoga ep., Mercurialis ep., Sida ep. Abutilon sp., Ambrosia sp., Xanthium ep., Cireium ep., Artemisia sp., Rumex sp., Convolvulus ep., Ipomea sp., Sinapis sp.

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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 up to the cotyledon stage, but then stop their growth and finally die off completely after three to five weeks. Upon application of the active ingredients to the green parts of plants postemergence also occurs very quickly after the treatment, a dramatic growth stop • in, and the weed plants remain in the existing stage of application growth stage or die after a period of time more or less fast, so that on This way, a weed competition that is detrimental to the crop plants can be eliminated very early and sustainably by the use of the novel agents according to the invention.

Although the compounds of the present invention have excellent herbicidal activity against mono- and dicotyledonous weeds, crops of economically important crops such as e.g. 'Wheat, barley, rye, rice, maize, sugar beet, cotton and soya only marginally or not at all damaged. For these reasons, the present precursors are very well suited for the selective control of undesired plant growth in agricultural crops.

Moreover, the compounds according to the invention exhibit growth modulatory properties in crop plants. They regulate the plant's metabolism and can thus be used to facilitate harvesting, such as by triggering desiccation, abscission and stunted growth. Furthermore, I also use them for general control and inhibition of unwanted 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.

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The compounds according to the invention can, if appropriate in admixture with further active components, be used as wettable powders, emulsifiable concentrates, sprayable solutions, mordants, dusts, 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 (s) except, if appropriate, a diluent or inert substance or wetting agent such as polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenylsulphonates and / or dispersing aids such as lignosulphonic acid sodium, 2,2 '. -dir.aphthylmethane-6,6 ¹ -disulfonate sodium, dib'utylnaphthalenesulfonic acid sodium or oleoylmethyltaurine "" sodium. The preparation takes place in common catfish, for example by grinding and mixing the components.

Emulsifiable.concentrates can be prepared for example by dissolving the active ingredients in an inert organic solvent such as butane oil, cyclohexanone, dimethylformamide, xylene or higher-boiling aromatics or aliphatic or cycloaliphatic hydrocarbons with the addition of one or more emulsifiers. at

liquid active ingredients, the solvent content can also be completely eliminated cder 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 condensation products, alkyl polyglycol ethers, sorbitan acid esters, polyoxethylenesorbitanic acid esters or polyoxethylenesorbitol esters.

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Dusting agents can be obtained by grinding the active ingredients with finely divided, solid materials, e.g. Talc, natural clays such as kaolin, bentonite, fyrophillite or diatomaceous earth obtained.

Granules can either be prepared by atomizing the active ingredients onto adsorptive, granulated inert material or by applying active ingredient concentrations by means of binders, e.g. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils on the surface of carriers such as sand, kaolinites or granulated inert material. It is also possible to granulate suitable active ingredients in the manner customary for the preparation of fertilizer granules, if desired in admixture with fertilizers.

In wettable powders, the active ingredient concentration is about 10 to 90 wt .-%, the remainder to 100 wt .-% consists of conventional formulation components. For emulsifiable concentrates, the active ingredient concentration may be about 5 to 80% by weight. Dust shaped "? Formulations usually contain 0.05 to 20 wt .-% of active ingredient (s), sprayable solutions about 2 to 20 wt .-%. In granules, the active substance content depends in part on _r on whether the active compound is liquid or solid and which granulation auxiliaries, fillers etc. are used.

Danebon, the active substance formulations mentioned optionally contain the usual adhesion, wetting, dispersing, emulsifying, penetrating, dissolving, filling or carrier substances.

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For use, the concentrates present in commercial form are diluted, if appropriate, in general Weiiie,. z. B, for wettable powders "emulsifiable concentrates" dispersions and sometimes also for microgranulaton using water. Dusty and granulated preparations »owl sprayable solutions are no longer diluted with other inert substances before use.

With the external conditions such as temperature «humidity u. It varies within wide limits, eg between 0, GO5 and 10.0 kg / ha or more of active substance, but is preferably between 0.01 and 2 kg / ha.

Mixtures of the mixed formulations with other active substances, such as, for example, insecticides, acaricides, herbicides, fertilizers, growth regulators or fungicides, may also be possible.

The invention is illustrated by the following examples. Aueführung8bel8Plele A » Formulary information

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

A wettable powder which is readily dispersible in water is obtained by adding 25 parts by weight of active ingredient "64% by weight".

- 14a -

Parts containing kaolinhaltigen quartz as inert material, 10 weight points lignosulfonate potassium and 1 part by weight of oleoylmethyltaurineae sodium as wetting and dispersing and grinding in a pin mill.

, ₁₅ _ 2Ä4

A dispersion concentrate readily dispersible in water is obtained by mixing 20 parts by weight of active compound with 6 parts by weight of alkylphenol polyglycol ether (Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 AeO) and 71 parts by weight of paraffinic mineral oil (boiling range, for example, about 255 to more than 377 ^° C.) Grinded to a fineness of less than 5 microns in a ball mill.

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

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Chemical examples example 1

SM-chloro-S-ethoxycarbonyl-phenylW.g-dioxo-IS-diazabicyclo C4.3.0-p-n-anan-2-carboxylic acid (1-ethoxycarbonyl-ethyl-ester )

37.3 g (0.10 mol) of piperidine-2,6-bis-carbonsä "acid-b1 s- (1-ethoxycarbonyl-ethyl-ester) were dissolved in 200 ml toluene were given at 20 -. 3O ⁰ C 22.6 g (0.10 mol) of 4-chloro-3-ethoxycarbonyl-phenyl isocyanate dissolved in 50 ml of toluene was added dropwise.

After stirring for 1 h at room temperature was added at 3 h

80 ⁰ C stirred. After distilling off the solvent, the remaining solid was recrystallized from methanol. 39.5 g (82 % of theory ) of 8- (4-chloro-3-ethoxycarbonyl-phenyl) -7 were obtained. 9-dioxo -1. 8-diaza-bicyclo-C4. 3.03nonan-2-carboxylic acid-il-ethoxycarbonyl-ethyl ester) in the form of colorless crystals of melting point: 121 - 128 ⁰ C.

Example 2

8- (4-chloro-2-f1uor-5-methoxy-phenyl) -2-methyl-7.9-dioxo -1. S-diaza-bicycloQQ.3. CD ηon on

20 g (0.10 mol) of 4-chloro-2-fluoro-5-methoxyphenylisocyanate were added to 17 g of Ig (O, 10 mol) of ethyl 6-methyl-piperidine-2-carboxylate. dissolved in 100 ml of toluene, added dropwise.

The mixture was stirred at 100 ^° C. for 3 h. The solvent was distilled off under reduced pressure and dried under high vacuum to constant weight.

33.0 g (99 μl of th.) Of 8- (4-chloro-2-fluoro-5-) were obtained.

methoxy-phenyl) -2-methyl-7.9-di-oxo-l8-diazi> -bicyclo [4. 3.CQ nonan in the form of a light yellow syrup.

Example 3

8- (4-chloro-2-fluoro-5-methoxy-phen yl) -7,9-d1α-o8-diaza bieye Ιο-Ο * S.S.pnonan S -carboxylic acid ethyl ester

20.2 g (0.1 mol) of 4-chloro-2-fluoro-5-methoxyphenyl isocyanate, dissolved in 100 n l of 100, were dissolved in 150 ml of chlorobenzene (22.9 g, 0.1 mol) of diethyl piperidine- [B. Dicarboxylate] ml of chlorobenzene, added dropwise

The mixture was stirred for 3 h at 100 ⁰ C, the solvent was distilled off and dried under high vacuum to constant weight.

This gave 37.8 g (98 % of theory ) of 8- (4-chloro-2-fluoro-5-methylthoxy-phenyl) -7.9-dioxo-l. e-diaza-bicyclo-Ol.SiOnonan-S-carboxylic acid ethyl ester in the form of a honey-colored syrup.

Example 4

8- (4-chloro-2-fluoro-5-methoxyphenyl) -7.9-dioxo-l.4.8- triazabi eye Io (14.3 CQ nonane-S-carboxylic acid ethyl ester

To 11.5 g (0.05 mol) of diethyl piperazine S-dicarboxylate in 100 ml of toluene were added 10.1 g (0.05 mol) of 4-chloro-2-fluoro-5-methoxyphenylisocyanate dissolved in 70 ml of toluene. within 1 h at 20 ⁰ C added dropwise. The mixture was then stirred at 100 ⁰ C for 4 h and the solvent abdestil11ert. The remaining residue was triturated with hexane and filtered with suction. This gave 14.8 g (77 % of theory ) of 8- (4-chloro-2-fluoro-5-methoxyphenyl) -7.9-dioxo-1. 4.8-tr1azabicyclo-C4.3-ozone-5-carboxylic acid ethyl ester in the form of pale yellow

Crystals with melting point: 56 - 58 ⁰ C.

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Example 5

8 "Ci-ChTorpheny1) -7-imino-9-oxo-l, 8-di aza-bicyclof4, 3. CD η on a n

To 11.0 g (0.1 mol) of 2-cyanopiperidine in 80 ml of toluene was added dropwise 15.4 g (0.1 mol) of 4-chloro-orphenyl isocyanate dissolved in 50 ml of toluene. It was stirred for 4 h at 100 ⁰ C and the solvent was distilled off.

This gave 26.0 g (98 3! Of th.) Of 8- (4-chlorophenyl) -7-1mino-9-oxo-l .8-diaza-bicyclo (}}. 3.03nonane in the form of a light brown glassy mass ,

Example 6

8- (4-chloro-2-fluoro-5-methoxy-pheny1) -3.5-dimethyl-7.9-dioxo-4-oxa-1.8-diaza-bicycloC4.3.CDnonan

To 13.9 g (0.10 mol) of 3-cyano-2.6-dimethyl-morpholine in 100 ml of toluene were added 20.2 g (0.10 mol) of 4-chloro-2-fluoro-5-methoxyphenyl isocyanate dissolved in 100 ml of toluene , dripped.

The mixture was stirred at 100 ^° C. for 3 h. After addition of 50 ml of 20% aqueous hydrochloric acid was stirred for 2 h at 100 ⁰ C again.

The organic phase was separated, washed 2 × with 100 ml of water and dried over sodium sulfate.

The remaining after the removal of the solvent

sticky solid residue was triturated with diisopropyl ether.

This gave 26.4 g (77 % of theory ) of 8- (4-chloro-2-fluoro-5-methoxyphenyl) -3,5-dimethyl-7,9-dioxo-4-oxa-1,8-diaza bicycloC4.3.CQnonan in the form of colorless crystals melting point: 126-131 ⁰ C.

- 19 -

Example 7

8- (4-chloro-2-fluoro-5-methoxy-phenyl) -7.9-d1-oxo-3-thia -1,8-diaza-bicycloC4.3.CPnona n

To 17.5 g (0.10 mol) of 1 .S-Thiazan ^ -carboxylic acid ethyl ester in 150 ml of toluene were added 20.2 (0.10 n.ol) 4-chloro-2-fluoro-5-methoxyphenylisocyanate, dissolved in 50 ml of toluene, it was stirred for 4 h at 100 ⁰ C and the solvent was distilled off. The residual solid was triturated with di-1-propyl ether and dried.

24.9 g (75 % of theory) of 8- (4-chloro-2-fluoro-5-methoxy-phenyl) -7.9-dioxo-3-thla-1 were obtained. B-diaza-bicycloC.3. £) nonane 1n form pale yellow crystals of melting point:

55 - 61 ⁰ C.

Example 8

8- (4-Chloro-2-fluoro-5-propargyl-oxy-phenyl) -2- (1,3-dioxolan-2-yl) -7.9-dioxo-1. 8-diaza-b icyclof4 .3.0 * 3 η on

To 11.5 g (0.05 mol) of ethyl 6- (1,3-dioxolan-2-yl) -p1per1din-2-carboxylate in 100 ml of toluene was added 11.3 g (0.05 mol) of 4-chloro-2-fluoro 5-propargyloxy-phenyl isocyanate, dissolved in 50 ml of toluene, added dropwise. After 3 h stirring at 100 ⁰ C, the solvent was distilled off and dried to constant weight in a high vacuum. This gave 19.8 g (97 % of theory ) of 8- (4-chloro-2-fluoro-5-propewyloxy-phenyl) -2- (1,3-d1oxolan-2-yl) -7.9-d1-oxo 1.8-diaza-bicyclo (4.3.0 ^) nonane 1n form one? colorless glass.

Example 9

4_2 Benzyl-8- (4-chloro-2-fluoro-5-isopropoxy-p-t-enyl) -7.9- dioxo-1,4,8-triaza-bicyclone-4,3- olanone

To 12.4 g (0.05 mol) of ethyl 4-benzyl-piperazine-2-carboxylate in 100 ml of toluene was dissolved 11.5 g (0.05 mol) of 4-chloro-2-fluoro-5-isopropoxyphenyl isocyanate in 50 ml of toluene, added dropwise.

The mixture was stirred at 100 ^° C. for 3 h and the solvent was distilled off.

After drying under HV to constant weight, 30.7 g (96 parts of th.) Of 4-benzyl-8- (4-chloro-2-fluoro-5-1-sopropoxyphenyl) -7.9-dioxo were obtained. l .4 .8-tr1aza-b1cydoC4. 3.OQ nonan 1n form of a light yellow syrup.

HV * high vacuum Example 10

8- (4-chloro-2-fluoro-5-methoxy-phenyl) -7-oxo-9-th1oxo-1.8-d1aza-b1cyc1of4. 3.ff3nonan-2-carbonsa'ure- (2.2.2-tri- fluorethylester)

To 16.9 g (0.05 mol) of Piper1din-2.6 -ibTs ^ TT ^. 2-trifluoroethyl Jester In 150 ml of toluene was /. 10.9 g (0.05 mol) of 4-chloro-2-fluoro-5-methoxy-phenyl isothiocyanate dissolved in 70 ml of toluene, added dropwise and stirred at 100 ⁰ C for 6 h. After distilling off the solvent, the residue was triturated with η-hexane and dried. This gave 19.8 g (87 % of theory ) of 8- (4-chloro-2-fluoro-5-methoxyphenyl) -7-oxo-9-thioxo-1. . 8-diaza-b1cyc ^ o £ 4.3 © · on non-2-carbonsa υre- (. 2 2.2 Tr1-fluorethylester) 1n form of pale beige crystals, m.p. · 134-138 ⁰ C.

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28 biological examples

Damage to weed plants or crop tolerability was rated according to a key in which the efficacy is expressed by values of 0-5. Where:

0 = no effect

1 ss 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 nono- and dicotyledonous weed plants were placed in sandy loam soil in plastic pots and covered with soil. The compounds of 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 to 800 l / ha in different dosages.

After the treatment, the pots were placed in the greenhouse and kept under good growth conditions for the weeds. The visual assessment of the plant or the impact damage occurred after emergence of the test plants after a test period of 3-4 weeks compared to untreated controls. As shown by the scores in Table 2, the compounds of the present invention have good herbicidal pre-emergence activity against a broad spectrum of grass weeds and weeds.

964

2. weed effect postemergence

Seeds or rhizome pieces of monocotyledonous and dicotyledonous weeds were placed in sandy loam soil in plastic pots, covered with soil and grown in the greenhouse under good growth conditions. Three weeks after sowing, the test plants were treated at the trefoil stage.

The compounds according to the invention formulated as wettable powders or emulsion concentrates are sprayed onto the green parts of the plant in different dosages with a conversion rate of 600-800 l / ha, and the effect of the preparations after about 3-4 weeks' life of the test plants in the greenhouse under optimal growth conditions visually scored in comparison to untreated controls.

The compositions of the invention have a good herbicidal activity against a broad spectrum of economically important t ^T router and weeds (Table 3) and post-emergence.

Table 2 kg 2 dose STM herbicidal SIA effect ECG Pre-emergence 5 a.i./ha 5 CRS 5 LOM 5 Example no. 6 2 B 3 5 2 5 4 7 2.5 5 4 5 2 5 54 2.5 5 5 5 5 5 55 2.5 5 5 5 5 5 63 2.5 5 5 5 5 5 64 2.5 5 5 5 5 5 67 2.5 5 5 5 5 5 68 2.5 5 5 5 5 5 2.5 5 5 5 5 5 2.5 5 5

30

Table 3 Dose kg a.i./ha STM herbicides CRS SIA 5 Effect LOM ECG 2.5 5 5 5 5 5 postemergence 2.5 5 4 5 5 5 At game no. 2.5 5 4 5 5 4 2 2.5 5 5 3 5 5 6 2.5 4 3 5 3 4 7 2.5 5 4 5 5 3 54 2.5 4 3 5 4 4 55 2.5 4 5 5 3 3 63 2.5 5 5 5 5 64 67 68

Abbreviations: STM = Stellaria media CRS «Chrysanthemum segetum

SIA - Sinapis alba

LOM = LoIium multifiorum ECG = Echinochloa crus-galli

a.i. = Active substance

Claims (5)

claims 1 · Herbicidal agent, characterized in that «oils ale active substance compounds of the formula I or their salts Ar-Ii 1 T (I), wherein Ar "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, (C ₁ -C ₄ ) AIkVl, Halo ( C ₁ -C ₄₁ alkylene, (C ₁ -C ₄ ) alkoxy, (C ₃ -C ₆ , cycloalkoxy, (C ₁ -C 8) alkenyloxy, (C ₁ -C ₄ ) alkynyloxy, (C ₁ -C ₄ ) AIkOXy- (C ₁ -C ₄ -alkoxy, halo (C ₁ -C ₄ -alkoxy, halo (C ₃ -C ₆ -alkenyloxy, halo (C ₃ -C ₆ -alkynyloxy, (C ₁ -C ₄ -j. NO ₂ , -CW, -NHR ₁ , CyBnO (C ₁ -C ₄ ), phenoxy, phenoxy- (C ₁ -C ₄ J-BIkVl, PhOnVl (C ₁ -C ₄₎ alkoxy, phenylthio, phenylsulfinyl, phyllsulfonyl, where the six last-mentioned radicals in the phenyl radical may be substituted up to three times by halogen, (C ₁ -C ₄ -alkyl), (C ₁ -C ₄ -alkoxy, (C ₁ -C ₄ ) -alkoxycarbonyl, -CN or NO ₂ , or furthermore by a radical the formulas X / R ₁ AX 11 / | 5 \ / 1 -CZR ₄ , -O-P (XRg) ₂ or -Xi-Cj CZR ₄ may be substituted; R ₅ Zm -W- 264 R _{1 is} hydrogen, (C ₁ -C ₄ ) alkyl or phenyl which is substituted up to two times by halogen, (C ₁ -C ₄ ) AlHyI, (C ₁ -C ₄ ) -alkoxy, NO 2, CN or (C ₁ -C ₄ -alkoxycarbonyl can be, H2 »R3 are independently hydrogen, which may be substituted by cyano, hydroxy or (Cj-C4) alkoxy, phenyl or benzyl, both in the phenyl ring in each case preferably up to 2-fold by halogen, (Ci-C ₄ ) AllCyI, (C ₁ -C ₄ ) AIkOXy , NO 2 or -CN may be substituted; (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkoxycarbonyl, halide- ^) alkoxycarbonyl, (C ₁ -C ₄ ) -alkoxy (C ₁ -C ₄ ) -cycoxycarbonyl, (C ₁ -C ₄ -alkoxycarbonyl-C ₁ -C ₄ -alkoxycarbonyl, carboxy , or a remainder of the formulas / fi / Rn R ₁ / -C-N, -C-N-N, -C = N-N or R9 ^{& X} Fio ^N R11 R ₁ P4 is hydrogen, (C ₁ -C 4) alkyl, up to six times by halogen and / or up to disubstituted by (Ci-C ₄₎ alkoxy, (C ₁ -C ₄₎ -alkoxy (C ₁ -C ₄ JaIkOXy, (C ₁ -C ₄₎ alkoxycarbonyl, (C ^ C ^ alkylthio, (C ₁ -C ₄₎ A ^ yI-8ulfinyl, (C ₁ -C ₄₎ alkylsulfonyl, (C ₁ -C ₄₎ alkylamino, -CN, Puryl , Tetrahydrofuryl, benzofuryl, phenyl, phenoxy, benzyloxy, wherein in the six latter radicals each of the phenyl ring or the heteroaromatic substituted to zv., Three times by halogen, (C ₁ -C ₄ ) alkyl or (C ₁ -C ₄ ) alkoxy substituted eein may, (Cj-CgJCycloalkyl, (Cj-Cg) alkenyl, cyclohexenyl, (C3-C6) alkynyl, phenyl, which may be up to three-fold substituted by halogen, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) AIkOXy or (C ₁ -C ₄ ) alkoxycarbonyl; or  * - a remainder of the formula N * C ^R 13 5 the latter remainder being excluded for Z = S,
R5 is hydrogen or (C 1 -C 4) alkyl _; R 6 is hydrogen (C 1 -C 4) -alkyl or together with R 4 and the nitrogen atom connecting these radicals a 5- to 7-membered heterocycle which may contain one or two radicals of the group -O-, -S-, -NR 5 - as ring members and may be substituted up to 3 times by (C 1 -C 4) alkyl; Ry is hydrogen, (C 1 -C 4) -alkyl, phenyl or benzyl, where the phenyl ring can be substituted in each case up to three times by halogen, (C 1 -C 4) -alkyl, (C 1 -C 4) -alkoxy, (C 1 -C 4) -alkoxycarbonyl, NO2, CF3, -CN or a remainder of the formulas -CN. , -C-OR1, -C-Ri, -P (XR5) 2 or XR ₈ O 0 X -SR ₁ (S) _n R8 »Rg independently of one another are hydrogen or (C 1 -C 4) - alkyl or both R 3 and R 7 together with the nitrogen atom connecting them is a 5- to 7-membered heterocycle containing as ring members one or two radicals of the group -O -, -S-, -NR5- and up to three times by (Ci-C4) alkyl, hydroxy, (Ci-C4) alkoxy, phenyl or benzyl, both in Phenyl ring, preferably up to three times, may be substituted by (C 1 -C 4) -alkyl, (C 1 -C 4 -alkoxy, halogen or (C 1 -C 4) -alkoxycarbonyl, RiO » ^R 11 are independently hydrogen, Phenyl or benzyl, both of which may each be substituted in the phenyl ring, preferably up to three times, by halogen, (C 1 -C 4) -alkyl, (C 1 -C 4) -alkoxy, -NO 2, -CN, CF 3 or (C 1 -C 4) -alkoxycarbonyl, or Rj0 and R ^ together the rest R13 ^R 12 » ^R 13 independently of one another, (C 1 -C 4) -alkyl, (C 1 -C 4) -alkoxycarbonyl, phenyl or benzyl, which may both be substituted in the phenyl ring, preferably up to three times, by halogen, (C 1 -C 4) -alkyl, (C 1 -C 4) alkoxy, (C 1 -C 4) alkoxycarbonyl, CP 3, -CN or NO ₂ , R ₂ 0 0 M is -C, -S-, -S-, -3-, -O- or NR ₇ ; R3 0 Q ^S C, -S- or -0-
^ R ₅ .R ₂ OO T = C, -S-, -S-, -S- or -O-, R ₃ 0 964 844 T is CH ₂ , M may not be CH ₂ , S, SO or SO ₂ , in addition to the usual auxiliaries and carriers. » 2.Herbizida Agent according to claim 1, characterized in that it ale active compounds of the formula I, wherein Ar phenyl, which may be substituted up to three times by fluorine, chlorine or bromine, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy, (C ₃ -C ₄ ) alkenyloxy, (C ₃ - C ₄ ) alkynyloxy, halo (C ₁ -C ₄ ) a, alkyl, halo (C ₁ -C ₄ -alkoxy, -NHR ₁ , (C ₁ -C ₄ ) -alkylthio, (C ₁ -C ₄ ) -alkylsulfonyl, NO ₂ or a radical of the formulas -C-Z-R. odsr -X R ₁ β is hydrogen, (C ₁ -C ₄ alkyl, (C ₁ -C ₄ ) alkoxycarbonyl, R ₂ , R ₃ β independently of one another are hydrogen, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxycarbonyl, ( C ₁ -C ₄ ) alkoxy (C ₁ -C ₄ -alkoxycarbonyl, halogeno (C ₁ -C ₄ ) -alkoxycarbonyl, (C ₁ -C ₄ ) -alkoxycarbonyl (C ₁ -C ₄ ) -alkoxycarbonyl, -CN, carboxy, CN
⁰ -36- i 844 R ₄ * (C ₁ -C ₄ ) alkyl, holo (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxyalkyl, (C ₁ -C ₄ ) alkoxycarbonyl (C ₁ -C ₁ ) alkyl) ; R ₅ = H or (C ₁ -C ₄ ) aaryl R ₇ «hydrogen, (C ₁ -C ₄ ) alkyl, -CN i X ^ p ^K 9 Phenyl or benzyl, both of which may be substituted up to two times by (C ₄ -C.) Alkyl, (C ₄ -C.) Alkoxy, halogen, NO ₀ or -CF-substituted, Rg., Rq β hydrogen, (C ₁ -C ₄ ) Alkyl, together with the connecting N atom of a 6-membered saturated heterocycle M "C, -O- or -NR ₇ - ^R 3 3. Use of the compounds of the formula I according to claim 1 or 2 or their salt, characterized in that they are used as herbicides. 4. A method for controlling undesirable plants, characterized in that an effective amount of a compound of formula I or its 8aIz according to claim 1 or 2 applied to these or the agricultural soils · 5 »A process for the preparation of the compounds of formula I according to claim 1 or 2 or their salts, characterized in that a) for Y a o, S is a compound of formula II with a compound of formula III, ^R 2 HN
Ar-N = C = X Y = sC R ₁
OR TI III wherein R is H or (C ₁ -C ₄ ) alkyl, or b) reacting a compound of the formula II with an amine of the formula IV R ₂ R VL ³ . H-N M (IV) "Λ ⁰⁾ TJ V TJ, V! ^{b) maintaining} * ^ne compound is hydrolyzed For _mel I, and the erheltenen compounds are optionally converted into their salts.