NL8303084A - 5-PHENOXYBENZOIC ACID DERIVATIVES OF PENTITOLS, PROCESS FOR PREPARING THESE COMPOUNDS, AND CONTAINING THESE COMPOUNDS, AS HERBICIDE ACTING AGENTS. - Google Patents

Description

4. · -1- VO 5039 5-Phenoxyb etc. Acid acid derivative and pentitols, process for the preparation of these compounds, as well as these compounds containing herbicidally acting agents

The invention relates to new 5-phenoxybenzoic acid derivatives of pentitols, to a process for the preparation of these compounds, as well as to herbicidal agents containing these compounds.

Benzoic acid derivatives of pentitols with biological activity have hitherto not been known.

The object of the present invention is to provide new active compounds with beneficial action as a herbicide.

This problem is solved according to the invention by an agent which contains as new active compounds at least one 5-phenoxybenzoic acid derivative of pentitols of the general formula 1, in which one of the substituents Y is the group of the partial formula 1a and in each case two of the other substituents Y represent the group of the sub-formula 1b, in which R 1 and R 8 are the same or different from each other and each time hydrogen, a C 1 -C 20 Q alkyl radical, a single or multiple halogen, C C 1 -C 6 alkoxy, phenoxy and / or halophenoxy substituted C 1 -C 2 Q -alkyl radical, an aryl-C 1 -C 8 -slkyl radical, a single or multiple C 1 -C 8 alkyl, halogen, C 2 -C8 -alkoxy, nitro and / or trifluoromethyl-substituted aryl-C 1 -C 2 -alkyl radical, a C 1 -C 8 cycloaliphatic hydrocarbon Test, an aromatic hydrocarbon residue or a single or multiple C 1 -C 8 alkyl , halogen, C 1 -C 6 alkoxy, nitro and / or trifluoromethyl substituted aromatic carbon-hydrogen residue -or R 2 and Rg together with the adjacent the carbon atoms represent a C 1 -C 8 cycloaliphatic hydrocarbon residue, Z nitro, cyano or halogen, U hydrogen or halogen and 30 W hydrogen, halogen, cyano, trifluoromethyl or a C 1 -C 2 alkyl residue.

The agents according to the invention are surprisingly suitable at '/, -' - * * .. * 4 * -2- for controlling Tan weeds, even while conserving cultivated plants, and thus make the state of the art in this field considerably richer. .

The agents according to the invention are useful, for example, for the selective control of difficult to control weed grasses, such as Viola, Galium, Centaurea, Amaranthus, Ipomea, Fagopyrum, Sesbania, Datura, Chrysanthemum, Polygonum, Matricaria in cultures, such as soy, wheat, rice, barley, potatoes and potatoes.

The agents according to the invention can be administered before emergence, preferably after emergence, and advantageously already have a good effect even with small amounts of 0.05-5.0 kg of active substance / ha to be used.

The compounds according to the invention are distinguished by an optimum action of the indicated nature, in particular those representatives, in which the partial formula 1b of the general formula 11 R 1 and R 8 are the same or different and each time hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, 2,2-dimethyl-1-propyl, n-pentyl, n-heptyl, n-octyl, n-decyl, chloromethyl, bromomethyl, fluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, methoxymethyl, ethoxymethyl, phenoxymethyl, U-chlorophenoxymethyl, chloroethyl, bromoethyl, 2-ethoxyethyl, 2-phenoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl, benzyl, 2-phenylethyl 2-chlorophenyl, 3-chlorophenyl, h-chlorophenyl, 3, ij-dichlorophenyl, k-methoxyphenyl, 1-nitrophenyl or 2, U-dichlorophenyl.

The compounds of the invention having excellent activity are particularly those representatives, wherein in the general formula 11) Y ^ the group of the partial formula 1a and and Y ^ together and Y ^ and Y1. together each represent an optionally substituted methylene group of the formula Ib or 2) Y ^ the group of the general formula 2 and Y ^ and Y2 together and Y ^ 30 and Yj. together an optionally substituted methylene group or 3) Y? the group of the general formula II and Y ^ and Y ^ together and Y ^ and Y ^ together each represent an optionally substituted methylene group.

The compounds of the invention exist as optical, optionally also as geometric isomers. The individual isomers and their mixtures are also within the scope of the invention.

The compounds of the invention can be used either alone or in admixture with each other, or in admixture with other active compounds. If desired, defoliants, plant protection agents or agents to control harmful organisms may be used. be added according to the desired purpose.

5 If a broadening of the spectrum of action is envisaged, other biocides can also be added. For example, as herbicidally active mixture components, the active compounds are suitable, those described in Weed Abstracts, Volume 31, No. 7, 1982 under the title "List of common names and abriviations employd for currently used herbicides and 10 plant growth regulators in Weed Abstracts "are listed.

It is recommended that the active compounds according to the invention or their mixtures be in the form of preparations, such as powders, litters, granulates, solutions, emulsions or suspensions with the addition of liquid and / or solid carriers, respectively. diluents and, if desired, of wetting, bonding, emulsifying and / or dispersing agents, preferably in the form of emulsion concentrates.

Suitable liquid carriers are, for example, water, aliphatic and aromatic hydrocarbons, such as benzene, toluene, xylene, cyclohexanone, isophorone, dimethyl sulfoxide, dimethylformamide and further fractions of mineral oils.

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

Examples of surface-active compounds which may be mentioned are calcium lignin sulfonate, polyoxyethylene alkyl phenol ethers, naphthalene sulfonic acids and their salts, phenol sulfonic acids and their salts, formaldehyde condensation products, fatty alcohol sulfates, and substituted benzene sulfonic acids and their salts.

The content of the active compound (s) in the different preparations can vary within wide limits. For example, the agents may contain about 5-95 wt% active compounds, about 95-5 wt% liquid or solid carriers, and optionally up to 20 wt% surfactants.

The application of the agents can take place in the usual manner, for instance in amounts of about 100-1000 liters / ha to be sprayed with water as a carrier. The use of the agents in the so-called low-void and ultra-low-volume process is just as possible as their administration of Z 4 * * -lining in the form of so-called micro-granulates.

For the preparation of the preparations, the following ingredients are used, for example: A. Spray powder 5 a) 1 wt.% Wt. Active compound 25 wt.% Clay minerals 20 wt.% Colloidal silicic acid 10 wt. / Cell pitch 5 wt.% Surfactant substances based on a mixture of 10 bet calcium salt of lignin sulfonic acid with alkyl phenol polyglycol ethers b) 25 wt.% active compound 50 wt.% kaolin 10 wt.% colloidal silica 15 5 wt.% surfactants based on the sodium salt of N- methyl-oleyl-taurine and the calcium salt of lignin sulfonic acid c) 10 wt% active compound 60 wt% clay minerals 20 wt% colloidal silicic acid 10 wt% cell pitch and 5 wt% surfactants based on the sodium salt of N-methyl-N-oley 1-taurine and the calcium salt of lignin sulfonic acid 25 B. Paste 1 | 5 wt% active compound 5 wt% sodium aluminum silicate 15 wt% cetylpolyglycol ether with 8 mol ethylene oxide 2 wt% spindle oil 30 10 wt. % polyethylene glycol 23 parts water - TV *. "·«., A f.

* fr -5- C. Smulsconcertent a) 25 wt.% active compound 15 wt.% cyclohexanone 55 wt.% xylene 5 5 wt. # mixture of nonylphenylpolyoxyethylene or calcium dodecylbenzenesulfonate b) 10 wt. # active compound 6 wt. # cyclohexanone 36 wt. # xylene 10. 12 wt. # mixture of nonylphenylpolyoxyethylene or calcium dodecyl benzene sulfonate 36 wt. # mineral oil with high paraffin content

The new compounds according to the invention of the general formula 1 theirs are prepared according to a method known for analogous compounds.

The new compounds of the general formula I according to the invention can be prepared, for example, by: a) compounds of the general formula II, in which: one of the substituents I 'is hydrogen and 2 of the other substituents Y * each are the group of the partial formula 1b suggest reacting with compounds of the general formula 3, optionally in the presence of acid-binding agents and / or a catalyst, or b) compounds of the general formula b, in which one of the substituents Y '' is the group of the partial formula ba and in each case 2 of the other substituents Y ”represent the group of the partial formula 1b, in the presence of acid binding agents and / or catalyst, to be reacted with compounds of the general formula 5 wherein Bj, Z, U and W have the above meanings and X represent a halogen atom, preferably a chlorine or bromine atom.

The reaction components are reacted between -10 and 150 ° C, but generally between ambient temperature and reflux temperature of the respective reaction mixture. The reaction time is :: ::-3 * * 6 1- 1- 1-72 hours. As a rule, the reaction takes place at normal pressure or low overpressure. The reactants are used in approximately equimolar amounts to synthesize the compounds of the invention. Suitable reaction media are solvents inert with respect to the reactants. The choice of the solution or resp. suspending agents is aimed at the application of the. concerning alkyl, respectively. acyl halides and the acid acceptors used. As a solution or resp. suspending agents can be mentioned, for example: aliphatic and aromatic hydrocarbons, such as petroleum ether, cyclohexane, hexane, heptane, benzene, toluene, xylenes; halogenated hydrocarbons, such as methylene chloride, ethylene chloride, chlorobenzene, chloroform, carbon tetrachloride, tetrachlorethylene; ethers such as diethyl ether, diisopropylether, anisole, dioxane, tetrahydrofuran; carboxylic acid aerriles, such as acetonitrile, propionitrile, carboxylic acid amides, such as dimethylformamide; dimethyl sulfoxide; ketones such as acetone, diethyl ketone, methyl ethyl ketone; alcohols such as methanol, ethanol, propanol, butanol and mixtures of such solvents with each other. In some cases, the reactant itself can also serve as a solvent.

Suitable acid acceptors are organic bases such as, for example, triethylamine, trimethylamine, N, H-dimethylaniline, pyridine and pyridine bases (U-dimethylaminopyridine) or inorganic bases, such as oxides, hydroxides, earbonates, hydrogen carbonates and alcoholates of alkalis. and alkaline earth metal, as well as alkali metal salts of carboxylic acids (KOH, NaOH, Ka 2 CO 2, CH 2 COONa).

Liquid bases, such as pyridine, can be used simultaneously as a solvent. Hydrogen halide that may be formed can in some cases also be removed from the reaction mixture or by adsorption on a molecular sieve by passing an inert gas, for example nitrogen.

The presence of a reaction catalyst can be advantageous. Suitable catalysts are potassium iodide and onium compounds, such as quaternary ammonium, phosphonium and arsonium compounds, as well as sulfonium compounds. Polyglycol ethers, in particular cyclic, such as, for example, 18-crown-6, and tertiary amines, such as, for example, tributyl-35 amine, are also suitable. Preferred compounds are quaternary ammonium compounds, such as, for example, benzyl triethyl ammonium chloride and tetrabutyl ammonium bromide.

f: 3 jö 034 * -7-

The compounds of the invention prepared according to the above processes can also be isolated from the reaction mixture by conventional methods, for example, by distilling off the solvent used at normal or reduced pressure, by precipitation with water or by extraction. An increased degree of purity can generally be obtained by column chromatographic purification, as well as by fractional distillation.

As a rule, the compounds according to the invention are practically colorless and odorless liquids, which are also partly crystalline bodies, which are sparingly soluble in water, are sparingly soluble in aliphatic hydrocarbons, such as petroleum ether, hexane, pentane and cyclohexane, well soluble In halogenated hydrocarbons such as chloroform, methylene chloride and carbon tetrachloride, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, tetrahydrofuran and dioxane, carboxylic nitriles such as acetonitrile, ketones such as acetone, alcohols such as methanol and ethanol carboxylic acid amides, such as dimethyl foimamide and sulfoxides, such as dimethyl sulfoxide.

The starting compounds for the preparation of the compounds according to the invention are known per se or can be prepared by methods known per se.

The following examples serve to illustrate the preparation of the pentitol esters of the invention.

Example I

5-0- [5- (2-chloro-trifluoromethyl-phenoxy) -2-nitro-benzoyl] -1,2: 3, U-bis-0-25 (isopropylidene) -xylitol_

U0.0 g (0.172 mol) of 1.2: 3, 15-0- (isopropylidene) -xylitol in 250 ml of methylene chloride were started from, to which was added 17.3 δ (0.172 mol) of triethylamine at 20 ° C. Then, a solution of 65.3 g (0.172 mol) of 5- (2-chloro-30 h -trifluoromethyl-phenoxy) -2-nitro-benzoyl chloride in 100 ml of methylene chloride was added dropwise therewith under ice-cooling at 20 ° C. Afterwards stirring was continued for 1 hour at ambient temperature. The reaction mixture was then washed 3x with 250 ml of water each time. After drying the methylene chloride phase with magnesium sulfate, it was filtered and the solvent was filtered off. The residual oil was digested with 500 ml of hot hexane, after which the hexane phase was again concentrated. The oil thus obtained was dried at 50 ° C / 0.1 torr (= 0.1 x 133.322 Pa) and then gradually crystallized, η ”1 1 Λ. Q ü • ·., · J -8-

Yield = 61.2 g = 62.4 # of the theory.

Melting point: 100-102 ° C

DC: running liquid = toluene / ethyl acetate (1: 1) R. value: 0.61 f * 5 Analysis: calculated: C 52.13 $ H 4.37 # N 2.43 # Cl 6.15 / ¾

Found: C 52.28 # H 4.27 # K 2.66 # Cl 6.49 #

The other compounds of the invention could be prepared analogously:

Example_Came of the compound_Physical constant 10 II 1 -0- [5- (2-Chloro-trifluoromethyl-phenoxy) - 31 ^ 20: 1,5067 2-nitrobenzoyl] -2,3: 4,5-bis-O-isopropyl- idene-D-arabitol III 3-0- [5- (2-chloro-4-trifluoromethyl-phenoxy) - n ^ 20: 1,504o-2-nitrobenzoyl] -1,2: 4,5-bis-O-isopropyl- 15 idea-adonitol

IV 5-0- [5- (2-Chloro-4-trifluoromethyl-phenoxy) - melting point: 173 ° C

2-nitro-benzoyl] -1,2: 3,4-bis-0 - [(4-chlorophenyl) -methylene] -xylitol V 5-0- [5- (2-Chloro-4-trifluoromethyl-phenoxy) ) - ιη20: 1.5309 20 2-nitro-benzoyl] -1,2: 3,4-bis-0- (chloromethyl-methylene) -xylitol VI 5-0- [5- (2-Chloro-4 -trifluoromethyl-phenoxy) - n ^ 20: 1,4-998 2-nitro-benzoyl] -1,2: 3,4-bis-0-methyl-octyl-methylene) -xylitol 25 VII 5-0- [5 - (2-Chloro-4-trifluoromethyl-phenoxy) - n: 20: 1.5191 2-nitrobenzoyl] -1,2: 3,4-bis-O- (ethyl-methylmethylene) -xylit ol VIII 5-0- [5 - (2-Chloro-4-trifluoromethyl-phenoxy) - in 20: 1, 5123-2-nitrobenzoyl] -1,2: 3,4-bis-O- (diethylmethylene) -xylitol

IX 5-0- [5- (2-Chloro-4-trifluoromethyl-phenoxy) - melting point: 66-67 ° C

2-nitrobenzoyl] -1,2: 3,4-bis-0- (methylmethylene) -xylit ol

The following examples further illustrate the uses of the compounds of the invention, which took the form of the above compositions.

Example X.

In a greenhouse, the compounds according to the invention listed in the table below were emulsified in an amount of 3.0 kg of 4-0 active compound / ha in 500 liters of water / ha, on Viola and • - ~ λ r -9 -

Matricaria sprayed as test plants before and after emergence. Three weeks after the treatment, the treatment result was estimated, with 0 = no effect and 1 = destruction of the plants means 5.

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

Compounds according to the formula and the inventive invention are combined 1 o. Viola / Matricaria Viola / Matrica-5-0- [5- (2-Chloro-if-trifluoromethyl-phenoxy) -2-nitrobenzoyl-1 2: 3, b-bis- C- (isopropylidene) -xylitol bbbb 1-0- [5- (2-Chloro-b-trifluoromethyl-15-phenoxy) -2-nitrobenzoyl] -2,3: b, 5- bis-Q-isopropylidene-D-arabitol bbbb 3-0- [5- (2-Chloro-b-trifluoromethyl-phenoxy} -2-nitrobenzoyl] -1,2: b, 5-bis-O-isopropylidene adonitol b 1 bb 20 5-0- [5- (2-Chloro-b-trifluoromethyl-phenoxy) -2-nitrobenzoyi] -1,2: 3, b-bis-0- [(b-chlorophenyl) -methylene] -xylitol b 1+ bb 5-0- [5- (2-Chloro-b-trifluoromethyl-phenoxy) -2-nitrobenzoyl] -1,2: 3, b-bis-25- (chloromethyl-methylene) -xylitol bbbb 5-0- [5- (2-Chloro-b-trifluoromethyl-phenoxy) -2-nitrobenzoyl] -1,2: 3, b-bis-O- (methyl-ethyl-methylene) -xyliole bbbb 5-0- [5- (2-Chloro-b-trifluoromethyl-30-phenoxy) -2-nitro-benzoyl] -1,2: 3, b-bis- 0- (ethylmethylmethylene) -xylitol bbbb 5-0- [5- (2-Chloro-b-trifluoromethyl-phenoxy) -2-nitrobenzoyl] -1.2: 3, b-bis-O- (diethyl lmethylene) -xylitol b b b b 35 5-0- [5- (2-Chloro-b-trifluoromethyl-tenoxy) -2-nitrobenzoyl] -1,2: 3, b-bis- O- (methylmethylene) -xylitol b b b b

Example XI

In a greenhouse, the listed plates were mixed with the

J

% I i,%% i -10- reported compound in an amount of 0.1 hg of active compound / ha to be used. The compound was sprayed evenly over the plants as an emulsion with 500 liters of water / ha. The compound according to the invention showed a high selectivity 3 weeks after the treatment with an excellent action against the weeds.

co §

• Hg oS 3 H C

? h 3 o λ tö c ωα> m fl ^ -ρ · ηΟ ft-p

üS> J§3SceS'e '-> S O

• H ¢ 30 CÖ P CÖ CÖ <D (O h · Η -P <U + 5CÖC

",. ,. ,, k r * s Η · Η -P ö gjQpf-Pfl} WlS B n (ή

Compounds according to the -ph oh s cd o m -p 3 ^ u u ... .. on Hröoiftajteno-Htflocece invention satt> ü> o <jHraQ * a: cQtt; EHO <: <; 5-0- [5- (2-Chloro-ii-tri- 0 0 0 0 0 0 0 0 0 0 10 10 10 10 10 10 10 fluoromethylphenoxy) -2-10 nitrobenzoyl] -1.2: 3, k-bis -0- (isopropylidene) -xylitol 5-0- [5- (2-Chloro-Wtri- 0 0. 0 0 0 0 0 .0 0 0 10 10 10 10 10 10 fluoromethylphenoxy) -2-15 nitrobenzoyl] -1 , 2: 3, k-bis-0- (methyl-octyl-methylene) -xylitol η "Λ ^ -¾ V ^ ··

Claims (4)

12. Process for the preparation of 5-phenoxybenzoic acid derivatives of pentitols, characterized in that compounds according to any one of claims 1 to 11 are prepared according to a method known for analogous compounds. 13. Process for the preparation of 5-phenoxybenzoic acid derivatives of pentitols, characterized in that compounds according to any one of claims 1 to 11 are prepared by a) compounds of the general formula 2, in which one of the substituents Y 'is hydrogen and in each case two of the other substituents Y 'represent the group of the partial formula 1b, if desired in the presence of acid-binding agents and / or a catalyst, to react with compounds of the general formula 3 or b) compounds of the general formula Ij ·, in which to react one of the substituents YM the group of the partial formula Ua and in each case two of the other substituents YM the group of the partial formula 1b, in the presence of acid-binding agents and / or a catalyst, with compounds of the general formula 5, wherein R 1, R 8, Z, U and M have the above meaning and X represent a halogen atom, preferably a chlorine or bromine atom. 1U. Process for the preparation of a herbicidal agent, characterized in that one or more compounds according to one or more of claims 1-11 are introduced into a dosage form suitable for use as a herbicide. 15. Formed herbicidal agents obtained by the process according to claim 11. 16. Herbicidal agents according to claim 15, obtained using the method according to claim 12 or 13. η λ n ^ 4: \, · .. -j - · * *