DD299298A5 - NEW OXAZOLIDINONE AND THIONE AS PLANT REGULATORS - Google Patents

Abstract

3-phenyl-oxazolidin-2-one and 2-thione-5-carboxylic acid derivatives of the formula (I) below in all stereoisomeric forms are suitable for regulating plant growth. In this formula, X is oxygen or sulfur; A is COOR1, COSR1, COOM, CONR2R3 or COCl; R is hydrogen, halogen or mono-, di- or trihalomethyl; n for 1, 2 or 3; R1 is hydrogen, C1-C4-alkyl, C2-C6-alkenyl or C2-C6-alkynyl; R 2 and R 3 independently of one another represent hydrogen, C 1 -C 4 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 7 -cycloalkyl, aryl or heterocyclyl; or R2 and R3, together with the nitrogen atom to which they are attached, represent a saturated C3-C7 heterocycle optionally substituted up to three times by C1-C4 alkyl or C1-C4 alkoxy; and M is the equivalent of an alkali or alkaline earth metal cation or HN (R2) 3. The invention encompasses the preparation and use of these compounds. Formula (I)

Description

Il

wherein η and R have the meaning given in claim 1 and A 'Wr-COOR ₁ and R _{1 is} -C ₁ -C ₄ alkyl, converted in a known manner to free acids, and the acids then in a conventional manner to the salt or by reacting with a compound of formula VI wherein B is the radical of an alcohol, mercaptan or amine, to the ester, thioester or amide of formula I β.

10. A plant growth regulating agent, characterized in that in addition to carrier and / or other additives as the active ingredient, a 3-P ^u 9nyl-oxazolin-2-one or -2-thione-5-carboxylic acid derivative of the formula I according to claim 1 contains.

11. Composition according to claim 10, characterized in that it contains between 0.1% and 95% active ingredient of the formula I according to claim 1.

12. A method for inhibiting plant growth, characterized in that applying an active ingredient of the formula I according to claim 1 or an agent containing this active ingredient in an effective amount to the plants or their L.6bensraum.

13. The method according to claim 12, characterized in that applying an amount of active ingredient between 0.01 and 10 kg per hectare.

The present invention relates to novel 3-phenyl-oxazolidin-2-one and -2-thione-5-carboxylic acid derivatives in all 'stereoisomeric forms, processes for their preparation, these derivatives containing active ingredients as plant growth regulators and the use of these derivatives or the containing plant growth regulating agents.

U.S. Patent No. 4,013,445 discloses 1- (bis-trifluoromethylphenyl) -2-oxopyrrolidine-4-carboxylic acid derivatives as herbicides and for regulating plant growth.

The use of 1-phenyl-2-oxopyrrolidine-4-carboxylic acids and their derivatives which are unsubstituted on the phenyl nucleus or substituted by halogen atoms and / or a trifluoromethyl group is disclosed in French Patent 1,363,615 and US Pat. No. 3,136,620. known as active substances for influencing plant growth.

It has now been found that the 3-phenyl-oxazolidin-2-one and -2-thione-5-carboxylic acid derivatives according to the invention have very good plant growth-regulating properties in all stereoisomeric forms.

The inventively proposed 3-phenyl-oxazolidin-2-one and -2-thione-5-carboxylic acid derivatives correspond to the formula I.

wherein X is oxygen or sulfur;

A is -COOR ₁ , -COSR ₁ , -COO ⁰ M ⁵¹ , -CONR ₂ R ₃ or -COCl;

R is hydrogen, halogen, mono-, di- or trihalomethyl;

η is 1,2 or 3;

Ri is hydrogen, C, -C ₄ -alkyl, Cz-Ce-alkenyl or C 1 -C 6 -alkynyl; R ₂ and R ₃ independently of one another are hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₆ -alkenyl, C ₁ -C ₆ -alkynyl, C ₁ -C ₇ -cycloalkyl, aryl or heterocyclyl; or R ₂ and R ₃ together with the nitrogen atom to which they are attached form an optionally substituted up to three times by C, -C ₄ alkyl or C ₁ -C ₄ -alkoxy saturated 3- to 7-membered Heterocyclic which still another heteroatom selected from the group O, N and S, included

can, stand; and M® is the equivalent of an alkali or alkaline earth metal cation or HN ¹¹¹ IR ₂ I ₃ and their optically active isomers.

In these definitions, halogen is fluorine, chlorine, bromine or iodine.

Alkyl is to be understood as meaning straight-chain or branched alkyl, eg. For example, methyl, ethyl, n-propyl, i-propyl, η-butyl, i-butyl, sec-butyl or tert. Butyl.

By alkenyl is meant straight-chain or branched alkenyl; such as: vinyl, allyl, 2-propenyl, methallyl, 3-butenyl, 2-butenyl, 3-pentenyl, 2-methyl-4-pentenyl, 3-hexenyl.

In the definitions, alkynyl is to be understood as meaning straight-chain or branched alkynyl; z. For example: propargyl, ethynyl, 2-propynyl, 3-butynyl, 2-methyl-3-pentynyl, 1,2-dimethyl-3-butynyl.

Cycloalkyl is, for example, cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl or cycloheptyl, but preferably cyclopropyl, cyclopentyl or cyclohexyl.

As cations M® are in particular those of alkali metals such as lithium, sodium or potassium and alkaline earth metals such as magnesium or calcium into consideration. In particular, M ^{0 is} HN ⁰ IR ₂ I ₃ , where the substituents R _{2 may be} identical or different, or for the cations of sodium or potassium.

When Aden is amide radical CONR ₂ R ₃ , in particular the following radicals are preferred: -CONH ₂ , -CON (CH ₃ J ₂ , CON (C ₂ H _b ) ₂ ,

CH-CH · - ^ / ^(Rlt) m

-CON ^, -COnJcH.i, -CONH- '| , -CONH- · J * ·

^X C ₂ H ₅ CH ₃

/ v / v / v

-CONH- (y, -CONH- (y , -CONH- (* x)

(y, CONH (y

JI-Vm JI-V »> V ⁱⁿ

-CONH-ζ>, -CONH-J y , -CONH -.

\ = · Ti = · N ₀ /

wherein R _{4 is} halogen, C, -C ₃ alkyl, C ₁ -C ₃ -alkoxy; C 1 -C 1 haloalkoxy and m is 0,1,2 or 3.

Examples of heterocycles formed by the substituents R ₂ and R _3, alone or together with the nitrogen atom carrying them, are pyrrolidine, pyrrole, imidazole, pyrazole, piperazine, piperidine, morpholine, pyridine, pyrimidine, thiazole,

Thiomorpholine, triazines and triazoles. .

Examples of aryl are phenyl and naphthyl, which radicals are unsubstituted or substituted by up to four times by halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, nitro, cyano, carboxyl, carbamoyl, alkoxycarbonyl, alkylcarbonyl, alkylsulfonyl, sulfamoyl and alkylsulfamoyl.

Preferred compounds of the formula I are those in which A is IUr-COOR ₁ or -COO ^e M®. From this group are to be mentioned as individual compounds:

3- (3,5-Bis-trifluoromethylphenyl) oxazolidin-2-on-5-carboxylic acid,

Methyl 3- (3,5-bis-trifluoromethyl-phenyl) -oxazolidin-2-one-5-carboxylate and 3- (3,5-bis-trifluoromethyl-phenyl) oxazolidine-1-o-carboxylic acid tributylammonium salt.

Particularly effective groups of compounds of the formula I form the optically active compounds of the formulas (R) -I and

(R) - (I) ^Λ Υ (S) - (I)

wherein A and X have the meaning given under formula I. From this group, by their good biological effect, the compounds in the eye, in which Afür-COOR | or -COC ^ M® stands. Preferred individual compounds of the formulas (R) -I and (S) -I are:

B-IRI-S-IS.S-Bis-trifluoromethylphenyD-oxazolidine ^ -on-B-carbosuric acid, B-IRI-S-IS.B-bis-trifluoromethylphenyD-oxazolidine ^ -thicn-B-carboxylic acid methylstyrene, 5- (S. ) -3- (3,5-Bis-trifluoromethyl-phenyl) -oxazolidin-2-one-5-carboxylic acid and O-ISl-S-IS.B-bis-trifluoromethyl-phenoxy-oxazolidine-thione-B-carboxylic acid, methyl ester.

The compounds of the formula I according to the invention can be prepared in a manner known per se by reacting, in the case of the racemic compounds of the formula I, an aniline of the formula II

IjIH ₂ / \

wherein η and R have the same meaning under the formula I gobobone, with racemic glycidol ((±) -2,3-epoxy-1-propanol) of the formula III

O CH ₂ -CH-CH ₂ -OH I ""

converts to 1,2-propanediolanilide of the formula IV,

X "H-CH ₂ -CH-

X is NH-CH ₂ -CH-CH ₂ OH

Il

in which η and R have the meaning given under the formula I, this diol is then cyclized in a suitable solvent, in the presence of a base with diethyl carbonate to 3-phenyl-5-hydroxymethyloxazolidin-2-one of the formula V,

-CH ₂ OH

"Ύ

Il

in which η and R have the meaning given under the formula I, this compound is then oxidized with an oxidizing agent for the 3-phenyl-oxazolidin-2-one-5-carboxylic acid of the formula Ia,

Vl

COOH

/ Γ '

\ (la)

wherein η and R have the meaning given under the formula I, and this acid, if desired, in a manner known per se to the salt or by reacting with a compound of the formula Vl

H-B (VI)

where B is the radical of an alcohol, mercaptan or amine, to the ester, thioester or amide of formula I - converts,

• ·

/ γ

(Ib) I Il

wherein A, η and R have the meaning given under the formula I

 An ester of the formula Ic

(Ic)

i π

• \

wherein A 'is -COORi and R _{1 is} C, -C ₄ alkyl and η and R have the meaning given under the formula I, if desired, with 2,4-bis (4-methoxyphenyl) -1,3- dithia-2,4-diphosphethane-2,4-disulphide (Lawesson's reagent) or another reagent suitable for introducing the thioxo group into the 3-phenyl-oxazolidine-2-thione-5-carboxylic acid derivative of the formula Id,

s'V

/\ lld)

• \

wherein A ', η and R have the meaning given under formula Ic.

Suitable reagents for introducing the thioxo group are e.g. Phosphorus pentasulfide and derived therefrom Arylphosphinsulfide. Such reagents are for. In Tetrahedron 41, 5061-5087 (1985).

Reactions for the preparation of compounds of formula V are known and z. In Tetrahedron Letters 45 (1989) 1323-1326, Chimie Thorapeutique 1973, 324-327 or FR-A 2,458,547.

The oxidation of the 3-phenyl-5-hydroxymethyl-oxazolidin-2-one of the formula V to 3-phenyl-oxazolidin-2-one-5-cärbonsäure of formula la is carried out z. According to Jones (Fieser & Fieser, "Reagents for Organic Synthesis", John Wiley & Sons, N.Y. Vol.

p. 142ff.) Using chromic acid in an aprotic organic solvent at a low temperature between -10 ⁰ C to room temperature. Suitable solvents are ketones such as acetone, methyl ethyl ketone, acetophenone, cyclohexanone, dioxane or higher ethers such as tetrahydrofuran or dipropyl ether.

The optically active isomers of the formula I, represented by the sub-formulas (R) -I and (S) -I, likewise form an object of the present invention. They can be prepared in a manner known per se by using the above-described reaction route rr ^; t commercially available, optically active glycidol ((+ Mil or (-) - III) or a racemic 3-phenyl-oxazolidin-2-one-5-carboxylic acid of the formula la

COOH

9- \

/ X

Il

wherein η and R have the meaning given under the formula I, by the known per se method of fractional crystallization in the presence of a chiral auxiliary such as an optically active base, in particular an optically active 1-phenylethylamine in the optically active 5- (R) ( -) - 3-phenyl-oxazolidin-2-one-5-carboxylic acid of the formula (R) -Ia

COOH

/ Γ "

il j

wherein η and R have the meaning given under the formula I and the optically active 5- (S) (+) - 3-phenyl-oxazolidin-2-one-5-carboxylic acid of the forms! (S) -I a separates,

COOH

ö> Y

wherein η and R have the meaning given under the formula I, these isomers optionally in known manner in the definition of derivatives of the formula (R) -Ic and (S) -Ic

"ύ

(R) - (Ic) "] (S) - (Ic)

I II

in which A 'is -COORi and R _{1 is} CHVALIY and η and R have the meaning given under the formula I transferred to then reacting by reaction with a capable of introducing the thioxo reagent reagent, the corresponding compounds of formulas (R) -Id and (S) -Id

A ¹ A ¹

(R) - (Id)^a 1 (S) - (Id)

I i ¹ y

wherein A 'TUr-COOR ₁ and R is C ₁ -C ₄ -A ^ yI, and η and R have the meaning given under the formula I, which optionally subsequently in a known manner in the other definitions Derivatives of the formulas (R) -Ie and (S) -Ie

A Λ

O-·'

(R) - (Ie) ^S ? (You)

η η

wherein A, η and R has the meaning given under formula I, can be converted.

Suitable reagents for introducing the thioxo group are, for example, phosphorus pentasulfide and the arylthionophosphine sulfides derived therefrom. Such reagents are described in Tetrahedron 41, 5061-5087 (1985). 2,4-Bis- (4-methoxyphenyl) -1,3-dithia-2,4-diphosphetane-2,4-disulphide (Lawesson's reagent) has proven to be a particularly suitable reagent for introducing the thioxo group.

The transfer of the compounds of the formulas (R) -Ia and (S) -Ia in the derivatives of the formulas (R) -Ib or (S) -I b according to the invention takes place in a manner known per se, for example by B .:

- By reaction with alcohols RiOH, mercaptans R ₁ SH or amines R2R3NH according to known methods. The conversion of the racemic 3-phenyl-oxazolidine-2-thione-5-carboxylic acids of formula Ie and their optically active 'isomers of the formulas (R) -Ie and (S) -Ie in the other derivatives of the formula Ie according to the definition also takes place in a known manner, eg:

in the case of acid chlorides (A = -COCl)

by reaction of the free carboxylic acids with suitable chlorinating agents, such as thionyl chloride, oxalyl chloride, phosgene or PCI ₅ .

- amides (^ = -CO-NT)

* ^J R ₂

by reaction of the acid esters, acid chlorides or free carboxylic acids with amines HN

^X R3

in the case of thioesters (A = -COSR ₁ )

by reaction of the Säurechlorio'e with mercaptans HSR ₁ ;

- For alkali metal or alkaline earth metal salts

by reacting the free carboxylic acids with alkali metal or alkaline earth metal hydroxides, alcoholates or carbonates, such as Na, K, Li, Ca and Mg hydroxide, sodium and potassium methoxide and ethylate;

- with amine salts

by reaction of the free carboxylic acid with amines N (R ₂ Ia.

The invention also relates to plant growth-regulating agents which contain a novel active compound of the formula I, and to processes for inhibiting plant growth.

Plant growth regulators are substances which produce agronomically desirable biochemical and / or physiological and / or morphological changes in / on the plant.

The active substances contained in the agents according to the invention influence plant growth in different ways, depending on the time of application, dosage, mode of administration and environmental conditions. Plant growth regulators of the formula I can, for example, inhibit the vegetative growth of plants. This type of effect is of interest on lawns, in ornamental plants, in orchards, on Straßenböschungen, on sports and industrial plants, but also in the targeted inhibition of secondary drives such as tobacco. In agriculture, the inhibition of vegetative growth in cereals leads to reduced storage via a stalk reinforcement, similar agronomic effects are achieved in oilseed rape, sunflowers, maize and other crops. Furthermore, by inhibiting vegetative growth, the number of plants per area can be increased. Another application of growth inhibitors is the selective control of soil-covering plants in plantations or far-row crops by strong growth inhibition without killing these ground cover, so that the competition is switched off against the main crop, but the agronomically positive effects such as erosion prevention, nitrogen fixation and soil loosening are preserved.

By a method of inhibiting plant growth is meant controlling natural plant development without changing the genetically determined life cycle of the plant as a mutation. The method of growth regulation is applied to a developmental time of the plant to be determined in the individual case. The application of the active compounds of the formula I can be carried out before or after emergence of the plants, for example already on the seeds or seedlings, on roots, tubers, stems, leaves, flowers or other plant parts. This can be z. B. by applying the drug itself or in the form of an agent on the plants and / or by treatment of the nutrient medium of the plant (soil) happen.

The compounds of the formula I according to the invention are preferably used for growth inhibition in dicotyledonous cultures with postemergic administration.

The compounds of the formula I are used in unchanged form or, preferably, as an agent together with the auxiliaries customary in formulation technology and are therefore used, for. B. to emulsion concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and encapsulations in z. As polymeric materials, processed in a known manner. The application methods such as spraying, atomizing, dusting, scattering or pouring are chosen in the same way as the type of means according to the desired goals and the given conditions.

The formulations, d. H. the active substance of the formula I and optionally a solid or liquid additive containing agents, preparations or compositions are prepared in a known manner, for. B. by intimately mixing and / or grinding the active compounds with extenders, such as. B with solvents, solid carriers and optionally surface-active compounds (surfactants).

Suitable solvents may be: Aromatic hydrocarbons, preferably the fractions C ₈ to C ₁₂ , such as. As xylene mixtures or substituted naphthalenes, phthalic acid esters such as dibutyl or Dioctylphthalat, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketones such as cyclohexanone, strongly polar solvents such as N Methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and optionally epoxidized vegetable oils, such as epoxidized coconut oil or soybean oil or water.

As solid carriers, ζ. As for dusts and dispersible powders, natural minerals are generally used, such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. As granular, adsorptive granules are porous types such. As pumice, broken brick, sepiolite or bentonite, as non sorptive Trägormatorialien z. As Ca'cit or sand in question. In addition, a Violzahl of pregranulated materials of inorganic or organic nature, in particular dolomite or crushed plant residues can be used.

Suitable surface-active compounds, depending on the nature of the active compound of the formula I to be formulated, are nonionic, cationic and / or anionic surfactants having good emulsifying, dispersing and wetting properties. Surfactants are also surfactant mixtures.

Suitable anionic surfactants may be both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.

As soaps are the alkali, alkaline earth or optionally substituted ammonium salts of higher fatty acids (C10-C22), such as

z. As the Na or K salts of oleic or stearic acid, or of natural fatty acid mixtures, the. B. can be obtained from coconut or tallow oil, called. Furthermore, the fatty acid methyl taurine salts should be mentioned.

Frequently, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates.

The fatty sulfates or sulfonates are generally present as alkali, alkaline earth or optionally substituted ammonium salts and have an alkyl radical having 8 to 22 carbon atoms, wherein alkyl also includes the alkyl moiety of acyl radicals, for. For example, the Na or Cd SaIz the sign sulfonic acid, the Dodecylschwefelsäureesters or a fatty alcohol sulfate mixture prepared from natural fatty acids. These include the salts of sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2-sulfonic acid groups and a fatty acid radical having 8 to 22 carbon atoms. Alkylarylsulfonates are z. As the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or a naphthalenesulfonic acid-formaldehyde condensation product.

Furthermore, corresponding phosphates, e.g. Salts of the phosphoric acid ester of a p-nonylphenol (4-14) -ethylene oxide adduct or Phcspholipide in question.

Suitable nonionic surfactants are primarily polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which may contain 3 to 10 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols ,

Further suitable nonionic surfactants are the water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups of polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain, said compounds usually containing 1 to 5 ethylene glycol units per propylene glycol unit.

Nonylphenol polyethoxyethanols, castor oil polyethylene glycol ethers, polypropylene polyol / ethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. May be mentioned as examples of nonionic surfactants.

Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as the polyoxyethyl sorbitan trioleate.

The cationic surfactants are, above all, quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 carbon atoms as N-substituents and which have lower, optionally halogenated alkyl, benzyl or lower hydroxyalkyl radicals as further substituents. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, e.g. For example, stearyltrimethylammonium chloride or benzyldi (2-chloroethyl) ethylammonium bromide.

The surfactants commonly used in formulation technology are i.a. described in the following publications:

Mc Cutcheon's Detergents and Emulsifiers Annual MC Publishing Corp., Ridgewood, New Jersey, 1981;

H. Stäche, "Tensid-Taschenbuch", 2nd edition, C. Hanser Verlag, Munich, Vienna, 1981;

M. and J. Ash. "Encyclopedia of Surfactants", Vol., Ill., Chemical Publishing Co., New York, 1980-1981.

The agrochemical preparations generally contain 0.1 to 95%, in particular 0.1 to 80% active ingredient of the formula 1.1 to 99.9% of a solid or liquid additive and 0 to 25%, in particular 0.1 to 25% a surfactant.

In particular, preferred formulations are composed as follows: {% =% by weight).

Emulsifiable concentrates:

Active ingredient: 1 to 20%, preferably 5 to 10%

Surfactants: 5 to 30%, preferably 10 to 20%

liquid carrier: 50 to 94%, preferably 70 to 85%

Dusts:

Active ingredient: 0.1 to 10%, preferably 0.1 to 1%

solid carrier: 99.9 to 90%, preferably 99.9 to 99%

Suspension concentrates:

Active ingredient: 5 to 75%, preferably 10 to 50%

Water: 94 to 24%, preferably 88 to 30%

Surfactant: 1 to 40%, preferably 2 to 30%

Wettable powder:

Active ingredient: O.c ο! Ϊο0%, preferably 1 to 80%

Surfactant: 0.5 to 20%, preferably 1 to 15%

solid carrier: 5 to 99%, preferably 15 to 90%

granules:

Active ingredient: 0.5 to 30%, preferably 3 to 15%

solid carrier: 99.5% to 70%, preferably 97 to P5%.

While more concentrated products are preferred as a commodity, ν the end user generally uses diluted funds. The use forms can be diluted down to 0.001% of active ingredient. The application rates are generally 0.01 to 10 kg AS / ha, preferably 0.025 to 5 kg AS / ha.

The compositions may also contain other additives such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active ingredients to achieve special effects.

Horstollungsbelsplole

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

Example 1: Preparation of racemic 3- (3,5-bls-trifluoromethylphenyl) -5-carbo-cyano-oxaecollin-2-one

O - C00H P pCH ₂ OH

J I r> =.

jjl oxidation

^; -) AA

F ₃ C · ^κ _CF3 F3C · CF ₃

To a cooled to O ⁰ C solution of 24.7 g (0.075 mol) of 3- (3,5-bis-trifluoromethylphenyl) -5-hydroxymethyl-oxazolidin-2-one (prepared according to Chimie Therapeutique 1973,324-327, from 3 , 5-bis-trifluoromethylaniline and rac. Glycidol) in 500 ml of acetone is added dropwise with stirring 62 ml of chromosulfuric acid (3.25 molar CrOa and 5.29 molar H2SO4). After everything is added, it is allowed to stir for 14 hours at room temperature. Then, to the resulting green suspension, first 100 ml of isopropanol, then 11 ethyl ether and finally 11 brine. After the chromium salts have dissolved, the organic phase is separated off and the aqueous phase is extracted with ether. The organic phases are dried over magnesium sulfate and concentrated on a rotary evaporator. The residue gives 25.86 g of beige crystalline substance, which is recrystallized from ether / petroleum ether, 19.42 g of title product in the form of white crystals of melting point 165-169 ⁰ C results.

Example 2: Preparation of racemic 3- (3,5-bis-trifluoromethylphenyl) -5-methoxycarbonyl-oxazolidin-2-one O J-COOCH ₃ O -j-COOH

n-l 1 0 = · *

HIGH ₃

· 0 =

J _x ^ -CF ₃ F ₃ C- " _X ^ i

A mixture of 52.2 g (0.152 mol) of 3- (3,5-bis-trifluoromethylphenyl) -5-carboxy-oxazolidin-2-one (Example 1) and 77.8 g of ®Amberlyst resin (20-50 mesh, strongly acidic) in 600 ml of absolute methanol is refluxed for 2 hours and allowed to stand overnight. The resin is then filtered off with suction and the filtrate is concentrated on a rotary evaporator. The brown, oily residue is taken up in ethyl ether, washed neutral with sodium bicarbonate and then with water, dried over magnesium sulfate and concentrated to dryness.

50.9 g of crude SO.S-bis-trifluoromethyl-phenyl-S-methoxycarbonyl-oxazolidine-1-ene are isolated as an orange oil. This is dissolved in methylene chloride and stirred with silica. After fuming off the silica, the solution is evaporated to dryness and the residue is stirred well in petroleum ether. The resulting crystals are filtered off and dried in vacuo at 4O ⁰ C. This gives 45.9 g (84.5% of theory) of methyl ester in the form of white crystals, which melt at 71-74 ⁰ C. In an analogous manner, the compounds of Table 1 are prepared.

Table 1:

• ·

/ γ

(Ib)

Connection no. A R η (CF ₃ ) ₂ phys , ιaten 1:01 (R) -COOCH ₃ 3.5 (CFj) ₂ Mp. 86 ° 1:02 + -COOCH ₃ 3.5 (CF ₃ ) ₂ Mp. 71 - 74 ° 1:03 (S) -COOCH ₃ 3.5 (CF ₃ ) ₂ 1:04 (R) -COOH 3.5 (CF ₃ ) ₂ 1:05 (S) -COOH 3.5 (CFj) ₂ 1:06 + -COOH 3.5 Cl ₂ Mp. 165 - 169 ° 1:07 (R) -COOCH ₂ CH ₃ 3.5 Cl ₂ 1:08 (S) -COOCH ₂ CH ₃ 3.5 Cl ₂ 1:09 + -COOCH ₂ CH ₃ 3.5 F ₂ 1.10 (R) -COO-CH-CH ₃ 3.5 CH ₃ F ₂ 1.11 (S) -COO-CH-CH ₃ 3.5 CH ₃ F ₂ 1.12 + -COO-CH-CH ₃ 3.5 CH ₃ Br ₂ 1.13 (R) -COO-CH ₂ CH ₂ CH ₂ CH ₃ 3.5 Br ₂ 1.14 (S) -COO-CH ₂ CH ₂ CH ₂ CH ₃ 3.5 Br ₂ 1.15 ± -COO-CH ₂ CH ₂ CH ₂ CH ₃ 3.5 (CF ₃ ) ₂ 1.16 (R) -C00-t-CH9 3.5 (CF ₃ ) ₂ 1.17 (S ^ COO-tert-C ^ 3.5 (CF ₃ ) ₂ 1.18 + -COO-tert-Ci ₁ Hg 3.5 Mp. 137 - 139 ° 1.19 (R) -COOCH ₂ -CH = CH ₂ 3-Cl 1.20 (S) -COOCH ₂ -CH = CH ₂ 3-Cl 1.21 + -COOCH ₂ -CH = CH ₂ 3-Cl (CFj) ₂ 1.22 (R) -COOCH ₂ -C ^ CH 3.5

Table 1 ! (Continuation)

Connection no. A (R) -COi / CH ₃ (S) -COi / CH ₃ (R) -COO ⁰ Na® R η phys. data 1.23 (S) -COOCH ₂ -C = CH CH ₃ CH ₃ + -COt / (S) -COO®Na® 3.5 (CF ₃ ) z 1.24 + -COOCH ₂ -CsCH CH ₃ + -C00 ^Ö Na® 3,5 (CF ₃ ) 2 Oei 1.25 (R) -COOCH ₂ -CH = CH CH ₃ [(R) -COO ⁰ ] ²⁰ Ca ² ® 3.5 I ₂ 1.26 (S) -COOCH ₂ -CH = CH CH ₃ [(S) -COO ⁰ I ²⁰ Ca ²⁰ 3.5 I ₂ 1.27 + -COOCH ₂ -CH = CH 3.5 I ₂ CH ₃ 1.28 (R) -COOCH ₂ -C = C-CH ₃ 3-F 1.29 (S) -COOCH ₂ -C = C-CH ₃ 3-F 1.30 ± -C00CH ₂ -CsC-CH. 3-F 1.31 (R) -COCl 3,5 (CF ₃ ) ₂ 1:32 (S) -COCl 3,5 (CF ₃ ) ₂ 1:33 + -COCl 3,5 (CFj) ₂ 1:34 (R) -COSCH ₃ 3,5 (CF ₃ ) ₂ 1:35 (S) -COSCH ₃ 3.5 (CF ₃ ) z I 36 + -COSCH ₃ 3,5 (CF ₃ ) ₂ Sn.p. j4 - 56 ° 1:37 (R) -C0S-n-C, H9 2, 3, 5 F ₃ 1:38 (S) -COS-Ii-C ₁₁ H ₉ 2, 3, 5 F ₃ 1:39 + -COS-n-CuHg 2, 3, 5 F ₃ CH ₃ 1:40 3, 5 Cl ₂ 1:41 3, 5 Cl ₂ 1:42 3, 5 Cl ₂ 1:43 3, 5 (CFj) ₂ 1:44 3, 5 (CF ₃ ) ₂ 1:45 3, 5 (CF ₃ ) ₂ M.p. 105 ° c. 1:46 3, 5 F ₂ 1:47 3, 5 F ₂

Table 1 : (continued)

Connection no. A ι ± -COOH R η 5 5 F ₂ phys. Oei dates 1:48 [♦ -COO ⁰ I ²⁰ Ca ²⁰ + -CON ^ / 0 + -COOCH ₂ C = CH 3, 5 5 Cl ₂ Oei 1:49 (R) -COO ⁰ H (CH ₉ ) 3 , OCH ₃ + -COOCH ₂ CH = CH ₂ 3, 5 5 Cl ₂ Mp. 1:50 (S) -COO ⁰ N ¹ H (CH ₉ ) 3 + -CONH- ^ ^ · 3, 5 5 Cl ₂ Mp. 1:51 + -COO ⁰⁰¹ H (CH ₉ ) 3 ^X CH ₃ 3, 5 5 (CCl ₃ ) Z Mp. 1:52 (R) -COO ⁰⁰ IH ₁ , 3, 5 (CC1 ₃ ) ₂ 1:53 (S) -COO ⁰⁰ JH ₁₁ 3, 5 5 (CC1 ₃ ) ₂ Mp. 1:54 + -COO ⁰⁰ JH ₁ . 3, 3-Br - 1:55 (R) -CO-N ^) 5 Mp. CH ₃ ⁷ 5 Mp. 1:56 (S, co- <~> 3-Br 5 Mp. 1:57 ± -CO-N ⁷ / · 3-Br 1:58 (R) -CO-NH- ⁷ 4-CF ₃ 1:59 (S) -CO-NH- ' ⁷ 4-CF ₃ 1.60 4-CF ₃ (CFj) ₂ 1.61 3, (CF ₃ ) z 1.62 + -CO-NH- ⁷ 3, (CF ₃ ) ₂ 1.63 3, (CF ₃ ) z 65 - 72 ° 1.64 Ϊ ~ C0S -! 1 "" Ci (Hg 3, (CF ₃ ) ₂ 132 - 134 ° 1.65 + -COOCH ₂ CH = CH ₂ 3, 150 - 151 ° ± -COO ⁰ H ^ i nC ₁ .H ₉ ) ₃ (CF ₃ ) ₂ 1.66 + -CONH- · ⁷ \ 3, 50 - 52 ° Cl ₂ 1.67 3, Cl ₂ 158-160 ° 1.68 3, Cl ₂ 149-152 ° 1.69 3, 115-117 °

Formullerungsbelspiele:

Example F1: Formulation Surfaces for Active Ingredients of the Formula I {% = wt .-%)

a) Injection powder Active substance from Table 1 Na lignosulfonate Na lauryl sulfate Na diisobutylnaphthalenesulfonate Octylphenol polyethylene glycol ether (7-8 mol AeO) Superdisperse silica Kaolin

sodium chloride

a) b) c) 20% 50% 0.5 ° / 5% 5% 5% 3% - - - 6% 6% _ 2% 2% 5% 27% 27% 67% 10% _

59.5%

The active ingredient is well mixed with the additives and ground well in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.

b) emulsion concentrate a) b) Active ingredient from Table 1 10% 1% Octylphenolpolyethylenglykol- ether (4-5 moles of AeO) 3% 3% Calcium dodecylbenzenesulfonate 3% 3% castor oil polyglycol (36MoIAeO) 4% 4% cyclohexanone 30% 10% xylenes 50% 79% From this concentrate can by V thin with what serEmul c) dusts a) b) Active ingredient from Table 1 0.1% 1% talc 99.9% - kaolin _ 99%

Ready-to-use dusts are obtained by mixing the active ingredient with the carrier and grinding on a suitable mill,

d) extruder granules active ingredient from Table 1 Na lignosulfonate carboxymethyl cellulose kaolin

The active ingredient is mixed with the additives, ground and moistened with water. This Gemisoh is extruded and then dried in a stream of air.

a) b) 10% 1% 2% 2% 1% 1% 87% 96%

e) coating granules active ingredient from Table 1 polyethylene glycol (MW 200) kaolin

3% 94%

The finely ground active ingredient is applied evenly in a mixer to the kaolin moistened with polyethylene glycol. In this way, dust-free coating granules are obtained.

f) suspension concentrate active substance from Table 1 ethylene glycol nonylphenol polyethylene glycol ether (15MoIAeO)

Na lignin sulfonate carboxymethyl cellulose 37% aqueous formaldehyde solution silicone oil in the form of a 75% aqueous emulsion of water

The finely ground active substance is intimately mixed with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution with water.

a) b) 40% 5% 10% 10% 6% 1% 10% 5% 1% 1% 0.2% 0.2% 0.8% 0.8% 32% 77%

g) saline 5% Active ingredient from Table 1 1% isopropylamine octylphenol polyethylene glycol ether 3% (78MoIAeO) 91% water

Biological examples:

The following examples illustrate the effect of some compounds of the invention in plant growth-regulating experimental setups.

Example B1: Growth inhibition in tropical Bodondecker Legumlnosen (cover crops) The plants (eg Centrosema pubescens or Psophocarpus palustris) are in 4-cm peat pots with terrestrial (45%), peat (45%) and zonolite (10 %) multiplied by cuttings. The cultivation takes place in the greenhouse at a daytime temperature of 27 ⁰ C and a nighttime temperature of 23 ⁰ C. The lighting duration is at least 14 hours / day with an intensity of at least

About 50 days after sowing of the cuttings, the pots are placed in 13 cm pots, 4-5 plants / pot. After another 60 days, the plants are cut back to about 15 cm height and applied. They are sprayed with 0.3 to 3 kg of active ingredient / ha (usually formulated 25%) in aqueous spray mixture. The amount of water used is about 200l / ha.

4 weeks after the application, the experiment is evaluated. It is scored and weighed the new growth compared to the control and evaluated the phytotoxicity. In this experiment, the plants treated with the active compounds from Table 1 show a significant reduction of the new growth without thereby damaging the test plants.

Example B2: Growth regulation in soybeans

The plants (eg the variety Williams) are sown in 11 cm clay pots with soil (45%), peat (45%) and zonolite (10%) and in the climatic chamber at a daily temperature of 24 ⁰ C and a night temperature of 19 ³ C attracted. The illumination duration is 16 hours per day with an intensity of approx. 2900 lux.

About 24 days after sowing repotting is done in 18 cm pots, 2 plants / pot. After another 12 days and at the stage of 5-6 trifol. Leaves, the application takes place with up to 100g active ingredient / ha, usually formulated 25% ig and in aqueous spray mixture. The amount of water used is about 200l / ha.

About 4 weeks after the application the evaluation takes place. Compared to untreated control plants, the active compounds according to the invention from Table 1 cause marked growth inhibition without phytotoxicity.

Example B3: Selective Growth Inhibition of Oilseed Rape and Klee In Mals

The compounds of Table 1 are very well suited to selectively inhibit soil-covering plants in a maize crop and thus to eliminate the water and nutrient competition of the sub-sowing while maintaining the agronomically desirable effects of subsidence such as erosion protection, nitrogen fixation and reduction of soil compaction. This is checked for the crop combinations maize / white clover and maize / rapeseed as follows:

Corn 'Blizzard' is sown in 15 cm pots with soil and cultivated in the greenhouse at day / night temperatures of 22/19 ° C and a lighting period of at least 13.5 hours / day for postemergence application for 15 days, the pre-eminent application is one day after sowing.

Rape 'Bienvenue' is sown in 15 cm pots with soil, 7 days by day / night temperatures of 22/19 ⁰ C, then 17 days at 10/5 ⁰ C, then 7 days at 15/10 ⁰ C until Cultivated application.

White Clover 'Ladino' is grown in 15 cm pots with a mixture of terrestrial earth (60%), peat substrate (30%) and zonolite (10%) for 40 days at day / night temperatures of 21/18 ⁰ C and a minimum illumination duration of 13 , 5 hours dressed.

Fertilization and irrigation takes place in all hospitals as required, the application of the compound no. 1.01 (25% formulated) takes place in 2001 water / ha and application rates of 30 to 500g / ha. 28 days after application, the height of the new growth is measured and the effect in% growth inhibition compared to the untreated control shown. 100% effect means complete growth stop, 0% effect means growth like untreated control.

The tested compounds of Table 1 showed in this experiment, good inhibition of growth in kiee and oilseed rape, while the maize was not inhibited in growth.

Example B4: Selective growth inhibition of weeds in crops

The compounds of Table 1 are also capable of selectively inhibiting weeds in crop stands selectively and thus eliminating their competition without completely killing them. This is tested with the crops barley, wheat and corn and with the weeds Ipomoea purpurea, Solanum nigrum, Xanthium strumarium, Chenopodium album, Galium aparine, Veronica persica and Chrysanthemum leucanthemum as follows:

The said crops and weeds are grown in the greenhouse and sprayed in the 4-6-leaf stage with an aqueous suspension of the compounds of Table 1. The treated plants are cultivated further in the greenhouse. 15 days after treatment is evaluated and the growth inhibition in% indicated (Table 2). 0 = no growth inhibition, 100 = complete growth stop after treatment. As an example, the results for compound no. 1.02 (Table 1).

plants 60 Growth inhibition in% at (g active ingredient / ha) 125 250 500 1000 0 0 10 barley 0 0 0 0 0 wheat 0 0 0 0 0 Corn 0 0 70 90 90 Ipomoea 10 60 70 80 80 Solanum 0 40 80 80 90 Xanthium 10 40 30 70 70 Chenopodium 0 20 70 90 100 Galium 10 20 80 90 90 Chrysanthemum 40 60 60 80 90 Veronica 30 50

Claims (8)

1. 3-phenyl-oxazolidin-2-one and ^ -thione-S-carboxylic acid derivatives in all stereoisomeric f-forms of the formula I. ι s / Λ '"  \ wherein X is oxygen or sulfur;
A is -COOR ₁ , -COSR ₁ , -C00 ^ö M ^e , -CONR ₂ R ₃ or -COCl; R is hydrogen, halogen, mono-, di- or trihalomethyl; η is 1,2 or 3; R _{1 is} hydrogen, C ₁ -C ₄ alkyl, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl; R ₂ and R ₃ are independently hydrogen, C ₁ -C ₄ -alkyl, C ₂ -C 6 alkenyl, C ₂ -C ₆ -AIkJnYl, C ₃ -C ₇ cycloalkyl, aryl or heterocyclyl; or R ₂ and R ₃ together with the nitrogen atom to which they are attached, for a optionally up to three times by C ₁ -C ₄ -AlkYl or C ₁ -C ₄ alkoxy-substituted saturated 3- to 7-membered heterocycle, the another heteroatom selected from the group O, N and S may be included; and M® is the equivalent of an alkali or alkaline earth metal cation or HN® (R ₂ ) ₃ . 2. optically active compounds according to claim 1 of the formulas (R) -I and (S) -I • it I ii wherein A, n, R and X have the meaning given in claim 1. 3. Compounds of formula I according to claim 1, in which AfUr-COOR ₁ or COO ^e M®, R is halogen or trifluoromethyl and η is 1 or ² and R ¹ and M® have the meaning given in claim 1. 4. 3-phenyl-oxazolidin-2-one-B-carbor.säurederivate according to claim 1 in all stereoisomeric forms of the formula I b -A (/ Υ I Il • \ wherein A, η and R have the meaning given in claim 1. 5. S-phenyl-oxazolidine ^ -thione-B-carboxylic acid derivatives according to claim 1 in all stereoisomeric forms of formula Ie r ^A μ ι wherein A, η and R have the meaning given in claim 1. 6. A 3-phenyl-oxazolidin-2-one according to claim 1, selected from the group consisting of 3- (3, B-bis-trifluoromethylphenyl) -oxazolidin-2-one-B-carboxylic acid, S- ^ B- Bis-trifluoromethylphenyl-O-oxazolidine -on-B-carboxylic acid methyl ester, B-fRJ-S-piB-bis-trifluoromethyl-phenoxy-oxazolidine -on-B-carboxylic acid, B-i-R-SO-bis-trifluoromethyl-phenyl-oxazolidine-mono- B-carboxylic acid methyl ester, B-isl-SO.B-bis-trifluoromethylphenyl O-oxazolidine -on-B-carboxylic acid, B-ISJ - ^ - O -bis-trifluoromethyl-phenyl-oxazolidine -on-B-carboxylic acid methyl ester, S- B-bis-trifluorrnethylphenyO-oxazolidin ^ -one B carbonsäuretributylammoniumsalz. 7. A process for the preparation of a 3-phenyl-oxazolidin-2-one and a 3-phenyl-oxazolidin-2-thion of the formula I according to claim 1, characterized in that an aniline of the formula II IjIH ₂ wherein η and R have the meaning given in claim 1, with racemic glycidol ((±) -2,3-epoxy-1-propanol) of the formula III
ο CH ₂ -CH-CH ₂ -OH ("D converts to 1,2-Propandiolaniüd of formula IV, OH
! JIH-CH ₂ -CH-CH ₂ OH Il wherein η and R have the meaning given in ^A -> 1, this diol is then cyclized in a suitable solvent, in the presence of a base with diethyl carbonate to 3-phenyl-5-hydroxymethyloxazolidin-2-one of the formula V, 0 --CH ₂ OH Il wherein η and R have the meaning given in claim 1 and then oxidizing this compound with an oxidizing agent for the 3 · phenyl-oxazolidin-2-one-5-carboxylic acid of the formula Ia, COOH / \ (la) I Il wherein η and R have the meaning given in claim 1, and this compound, if desired, in known manner to the salt or by reacting with a compound of formula Vl H-B (VI) wherein B is the radical of an alcohol, mercaptan or amine, converted to the ester, thioester or amide of the formula I b, ? -ι ^ Y wherein A, η and R have the meaning given in claim 1. 8. A process for the preparation of S-phenyl-oxazolidin ^ -thione-B-carboxylic acid derivatives according to claim 1 of the formula Id ι
• · (Id) Il wherein η and R have the meaning given in claim 1 and A 'is -COORi and R _{1 is} Ci-C4-alkyl, characterized in that an S-phenyl-oxazolidin ^ -on-B-carboxylic acid derivative of the formula I c Ο-.-Α ' c / γ " • · • \ wherein A ', η and R have the meaning given above, with 2,4-bis (4-methoxyphenyl) -1,3-dithia-2,4-diphosphethan-2,4-disulfide (Lawesson's reagent) or another to implement the thioxo group suitable reagent. 9. A process for the preparation of S-phenyl-oxazolidin ^ -thione-B-carbon-säu: 3rivaten according to claim 1 of the formula Ie / \ Oe) Il • \ wherein A, η and R have the meaning given in claim 1, characterized in that a 3-phenyl-oxazolidin-2-thione-5-carboxylic acid derivative of the formula Id