NO834078L - 5-PHENOXYBENZO ACID DERIVATIVES OF PENTITES AND HERBICIDE AGENTS CONTAINING THESE - Google Patents

Description

The present invention relates to new 5-phenoxybenzoic acid derivatives of pentols, methods for producing these compounds as well as herbicidal agents containing these compounds.

Benzoic acid derivatives of pentols with biological effects were not previously known.

The aim of the present invention is to provide new active substances with an advantageous herbicidal effect.

This goal is achieved with an agent which, as a new active ingredient, contains at least one 2-phenoxypropionic acid derivative of pentols of the general formula

in which one of the substituents Y denotes the group and two of the other substituents Y denotes the group

in which R.j and R.sup.2 are the same or different and represent hydrogen,

a C 1 -C 1 Q alkyl radical, a C 1 -C 1 Q alkyl radical which is substituted with one or more substituents selected from halogen, -C 8 alkoxy, phenoxy and/or halophenoxy, an aryl C 1 -C 4 alkyl radical, an aryl -C1-C3 alkyl radical which is substituted with one or more substituents selected from C1-C8 alkyl, halogen, C1-C8 alkoxy, nitro and/or

trifluoromethyl, a C 1 -C 8 -cycloaliphatic hydrocarbon residue, an aromatic hydrocarbon residue or an aromatic hydrocarbon residue which is substituted with one or more substituents selected from C 1 -C 8 -alkyl, halogen, -C 8 -alkoxy, nitro and/or trifluoromethyl, or where and R 2 together with the adjacent C atom denotes a C 1 -C 8 cycloaliphatic hydrocarbon residue, Z denotes nitro, cyan or halogen, U denotes hydrogen or halogen and W denotes hydrogen, halogen, cyan, trifluoromethyl or a C 1 -C 2 -alkyl residue .

The new agent is surprisingly suitable for controlling weeds while sparing useful plants, thus significantly enriching the state of the art.

The new agent can, for example, be used for selective control of difficult-to-control weeds such as viola, galium, centaurea, amaranthus, ipomea, fagopyrum, sesbania, datura, chrysanthemum, polygonum, matricaria in crops such as soya, wheat, rice, barley, peanuts and potatoes.

The new agent can be applied in the pre-emergence method, but is preferably applied in the post-emergence method and already shows a very good effect in low application amounts of 0.5 to 5.0 kg of active substance/ha.

Among the new compounds, compounds of general formula I in which R^ and R£ are the same or different and denote 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, 4- chlorophenoxymethyl, chloroethyl, bromethyl, 2-ethoxyethyl, 2-phenoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl, benzyl, 2-phenylethyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-methoxyphenyl, 4-nitrophenyl or 2,4-dichlorophenyl.

New compounds with outstanding activity are likewise those of the general formula I in which

1) Y.j denotes the group

and Y2 and Y3 together and Y4 and Y5 together denote an optionally substituted methylene group 2) Y^ denotes the group of general formula II and Y^ and Y2 together and Y^ and Y^ together denote an optionally substituted methylene group, or 3) Y[- denotes the group of general formula III and Y^ and Y^ together and Y^ and Y^ together denote an optionally substituted methylene group.

The new compounds act as optical, possibly also as geometric isomers. The individual isomers and their mixtures are covered by the scope of the invention.

The new compounds can be used either alone, in a mixture with each other or with other active substances. Optionally, defoliating agents, plant protection agents or pesticides can be added depending on the desired purpose.

If a wider range of effects is desired, other biocides can also be added. As herbicidal active mixture partners, for example, the active substances indicated in Weed Abstracts, Vol. 31, No. 7 1982, entitled "List of common names and abbreviations employed for currently used herbicides and plant growth regulators in Weed Abstracts".

Appropriately, the new active substances or their mixtures are used in the form of preparations such as powders, flow agents, granules, solutions, emulsions or suspensions with the addition of liquid and/or solid carriers, respectively diluents and possibly wetting, binding, emulsifying and/or or dispersing aids, 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, dimethylsulfoxide, dimethylformamide and further mineral oil fractions.

Bom solid carriers are suitable mineral soils such as clay species, silica gel, talc, kaolin, attapulgus clay, limestone, silicic acid and plant products such as flour.

Examples of surfactants include calcium lignin sulfonate, polyoxyethylene alkyl phenol ether, naphthalene sulfonic acids and their salts, phenol sulfonic acids and their salts, formaldehyde condensates, fatty alcohol sulfates as well as substituted benzene sulfonic acids and their salts.

The proportion of active substance in the various preparations can be varied within wide limits. For example, the agent contains 5 to 95% by weight of active substance, 95 to 5% by weight of liquid or solid carriers as well as possibly up to 20% by weight of surfactants.

The application of the agent can be carried out in the usual way, for example with water carrying spray quantities of from 100 to 1000 l/ha. An application of the agent in the so-called Low-volume and Ultra-low-volume method is also possible as well as application in

form of so-called microgranules.

For the preparation of the preparations, e.g. the following components:

A. Spray powder

a) 40% by weight active substance

25 wt% clay minerals

20% by weight colloidal silicic acid

10% by weight cell pitch

5% by weight surfactant based on a mixture of the calcium salt of ligninsulfonic acid with alkylphenol polyglycol ether

b) 25% by weight active substance

60% by weight kaolin

10% by weight colloidal silicic acid

5% by weight surfactant based on the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of ligninsulfonic acid

c) 10% by weight active substance

60 wt% clay minerals

15% by weight colloidal silicic acid

10% by weight cell pitch

5% by weight surfactant based on the sodium salt of N-methyl-N-oleyl-taurine and the calcium salt of ligninsulfonic acid

B. Pasta

45% by weight active ingredient

5% by weight sodium aluminum silicate

15% by weight of cetyl polyglycol ether with 8 mol of ethylene oxide

2% by weight spindle oil

10 wt% polyethylene glycol

23 parts water

C. Emulsion concentrate

a) 25% by weight active substance

15% by weight cyclohexanone

55% xylene by weight

5% by weight mixture of nonylphenylpolyoxyethylene or calcium dodecylbenzene sulphonate

b) 10% by weight active ingredient

6% by weight cyclohexanone

36% by weight xylene

12% by weight mixture of nonylphenylpolyoxyethylene or calcium dodecylbenzenesulfonate 36% by weight mineral oil with a high paraffin content

The new compounds of general formula I can, for example, be prepared by

a) compounds of general formula

in which one of the substituents Y<1> denotes hydrogen and two of the other substituents Y' denotes the group is reacted with compounds of the general formula

optionally in the presence of acid binding agents and/or a catalyst, or

b) compounds of general formula

in which one of the substituents Y'<1> denotes the group and two of the other substituents Y<1>' denotes the group is reacted with compounds of general formula

in the presence of acid-binding agents and/or a catalyst,

in which , R 2 , Z, U and W have the meanings given above and X denotes a halogen atom, preferably a chlorine or bromine atom.

The conversion of the reaction partners takes place between -10 and 150°C, generally between room temperature and the reflux temperature for a corresponding reaction mixture. The reaction duration is 1 to 72 hours. As a rule, the reaction takes place at normal pressure or slight overpressure. For the production of the new compounds, the reactants are used in equimolar quantities. Suitable reaction media are solvents inert to the reactants. The choice of solvent or suspending agent depends on the addition of the corresponding alkyl or acyl halide and the acid acceptor used. Examples of aliphatic and aromatic hydrocarbons such as petroleum ether, cyclohexane, hexane, heptane, benzene, toluene, xylene can be mentioned as solvents or suspending agents; halogenated hydrocarbons such as methylene chloride, ethylene chloride, chlorobenzene, chloroform, tetrachlorocarbon, tetrachloroethylene; ethers such as diethyl ether, diisopropyl ether, anisole, dioxane, tetrahydrofuran; carboxylic acid nitriles 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. In some cases, the reaction partner itself can also serve as a solvent.

Organic bases such as e.g. triethylamine, trimethylamine, N,N-dimethylaniline, pyridine and pyridine bases (4-dimethylaminopyridine) or inorganic bases such as oxides, hydroxides, carbonates, hydrogen carbonates and alcoholates of alkali and alkaline earth metals as well as alkali salts of carboxylic acids (KOH, NaOH, Na2C03 , CH-jCOONa) .

Liquid bases such as pyridine can also be used as a solvent. Formed hydrogen halides can in many cases also be removed from the reaction mixture by means of discharge with an inert gas, such as e.g. nitrogen, or absorbed on molecular sieves.

The presence of a reaction catalyst can be beneficial. As catalysts, potassium iodide and onium compounds are suitable, as are quaternary ammonium, phosphonium and arsonium compounds as well as sulfonium compounds. Also suitable are polyglycol ethers, in particular cyclic ones, such as e.g. 18-crown-6, and tertiary amines such as e.g. tributylamine. Preferred compounds are quaternary ammonium compounds such as e.g. benzyltriethylammonium chloride and tetrabutylammonium bromide.

Compounds produced according to the methods indicated above can be isolated from the reaction mixture by usual 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 usually be achieved by column chromatographic purification as well as by fractional distillation.

The new compounds are usually almost colorless and odorless liquids that are poorly soluble in water, relatively poorly 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 acid nitriles such as acetonitrile, ketones such as acetone, alcohols such as methanol and ethanol, carboxylic acid amides such as dimethylformamide, and sulfoxides such as dimethylsulfoxyd.

The starting compounds for the production of the new compounds are known in and of themselves or can be produced according to known methods.

The following examples illustrate a preparation of the new pentole esters.

Example 1

5-0-[5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitro-benzoyl]-1, 2:3,4-bis-0-(isopropylidene)-xylitol

40.0 g (0.172 mol) of 1,2:3,4-bis-O-(isopropylidene)-xylitol was introduced into 250 ml of methylene chloride and at 20°C was added

17.3 g (0.172 mol) of triethylamine. A solution of 65.3 g (0.172 mol) of 5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitro-benzoyl chloride in 100 ml of methylene chloride was then added dropwise under ice-cooling at 20°C. The reaction mixture was stirred for one hour at room temperature. The reaction mixture was then washed three times, each time with 250 ml of water. After drying the methylene chloride phase over magnesium sulfate, this was filtered and the solvent was removed. The remaining oil was triturated with 500 ml of hot hexane and the hexane phase was then evaporated. The oil obtained was dried at 50°C/0.1 torr and was then crystallized.

Yield: 61.2 g = 62.4% of theoretical

M.p.: 100-102°C

DC: Propellant = toluene/acetic ester (1:1)

Rf value: 0.61

In an analogous manner, the following compounds were prepared:

The following examples illustrate the application possibilities for the new compounds in the form of the previously indicated preparations.

Example 10

In greenhouses, the new compounds indicated in the table were sprayed in a quantity of 3.0 kg active substance/ha emulsified in 500 1 water/ha on viola and matricaria as test plants by the pre- and post-emergence method. Three weeks after the treatment, the treatment results were assessed, whereby 0 = no effect and 4 = destruction of the plants. As can be seen from the table, destruction of the test plants was achieved.

Example 11

In a weight house, the specified plants were treated after emergence with the specified compounds in a quantity of 0.1 kg of active substance/ha. For this purpose, the compounds were sprayed on as emulsions with 500 1 water/ha evenly over the plants. Three weeks after treatment, the new compounds showed a high selectivity with an outstanding effect against weeds.

Claims (7)

1. 5-phenoxybenzoic acid derivatives of pentols of general formula in which one of the substituents Y denotes the group and two of the other substituents Y denote the group wherein R 1 and R 2 are the same or different and represent hydrogen, a Cj -Cj Q -alkyl radical, a -C^Q -alkyl radical which is substituted with one or more substituents selected from halogen, Cj -Cg - alkoxy, phenoxy and/or halophenoxy, an aryl-C^ -C -C -alkyl radical . . atom denotes a C 1 -C 8 cycloaliphatic hydrocarbon residue, Z denotes nitro, cyan or halogen, U denotes hydrogen or halogen and W denotes hydrogen, halogen, cyan, trifluoromethyl or a C 1 -C 2 -alkyl residue. 2. 5-phenoxybenzoic acid derivatives of pentols according to claim 1, characterized in that and R2 are the same or different and denote 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, 4-chlorophenoxymethyl, chloroethyl, bromethyl, 2-ethoxyethyl, 2-phenoxyethyl, cyclopropyl, cyclopentyl, cyclohexyl, benzyl, 2-phenylethyl, phenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 3,4-dichlorophenyl, 4-methoxyphenyl, 4-nitrophenyl or 2,4-dichlorophenyl. . 3. 5-phenoxybenzoic acid derivatives of pentols according to claim 1, characterized in that these are 5-0-[5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoyl]-1,2:3,4-bis- 0-(isopropylidene)-xylitol, or 1-0-[5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoylJ-2,3:4,5-bis-O-isopropylidene-D- arabitol, or 3-0-[5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoyl]-1,2:4,5-bis-O-isopropylidene-adonitol, or 5-0-[5 -(2-chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoyl]-1,2:3, 4-bis-0-[(4-chlorophenyl)-methylene]-xylitol, or 5-0-[ 5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoyl]-1,2:3,4-bis-0-(chloromethylmethylene)-xylitol, or 5-0-[5-(2-chloro- 4-trifluoromethyl-phenoxy)-2-nitrobenzoyl]-1,2:3,4-bis-0-(methyl-octyl-methylene)-xylitol, or 5-0-[5-(2-chloro-4-trifluoromethyl -phenoxy)-2-nitrobenzoyl] - 1,2:3,4-bis-0-(ethylmethylmethylene)-xylitol, or 5-0-[5-(2-chloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoyl ] -1,2:3,4-bis-0-(diethylmethylene)-xylitol, or 5-0-[5-(2-chloro-4-trifluoromethyl-phenoxy )-2-nitrobenzoyl]-1 ,2:3,4-bis-O-(methylmethylene)-xylitol. 4. Process for the production of 5-phenoxybenzoic acid derivatives of pentols according to claims 1 to 3, characterized by ata) compounds of general formula in which one of the substituents Y' denotes hydrogen and two of the other substituents Y' denote the group reacted with compounds of general formula optionally in the presence of acid binding agents and/or a catalyst, or b) compounds of general formula in which one of the substituents Y <1> ' denotes the group and two of the other substituents Y'' denotes the group is reacted with compounds of general formula in the presence of acid-binding agents and/or a catalyst, in which R.j , R~ , Z' U and W has the meanings given above and X denotes a halogen atom, preferably a chlorine or bromine atom. 5. Agent with herbicidal effect, characterized in that it contains at least one compound according to claims 1-3. 6. Agent with herbicidal effect according to claim 5, in mixture with carrier and/or excipients. 7. Agent with herbicidal effect according to claim 5, produced according to the method according to claim 4.