CS238397B2 - Herbicide and method of its effective substance production - Google Patents

Description

The present invention relates to novel 5-phenocybenzoic acid pentite derivatives, to a process for the preparation of these compounds, and to compositions containing them having herbicidal activity.

So far, pentanoic benzoic acid derivatives with biological effects have not been known.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel active ingredient with a preferred herbicidal action.

According to the invention, this object is achieved by a composition comprising, as a new active substance, at least one pentite derivative of the 2-phenoxybenzoic acid of the formula I

CH. — O — Yt

AND

CH-O-Y,

I '

CH — OOY ₃

CH — O — Y4

AND

CH 2 -O-Y 5 wherein (I) one of Y is a group of formula II

and in each case two other substituents Y represent a group

where

R @ 1 is hydrogen or alkyl having 1 or 2 carbon atoms,

R 2 represents an alkyl radical having 1 to 8 carbon atoms, chloromethyl or chlorophenyl.

The compositions according to the invention are suitable for controlling weeds with surprising effect, even in the treatment of crop plants and hence. they desirable enrich the prior art in this field.

The compositions of the invention are, for example _; useful for selectively controlling hard-to-control weeds such as Viola, Galium, Centaurea, Amaranthus, Ipomea, Fagopyrum, Sesbania, Datura, Chrysanthemum, Polygons and Matricaria in cultures such as soy, wheat, rice, barley, peanuts and potatoes.

The composition of the invention may be applied by a pre-emergence, but preferably post-emergence process.

The composition preferably has a good effect even in small amounts of from 0.05 to 5.0 kg of active ingredient per hectare.

Compounds of the invention exhibit optimum activity mentioned type particularly when in formula I, R and R ₂ are the same or different and each denote hydrogen, methyl or ethyl, or R @ _t is as defined herein and R ₂ represents propyl, isopropyl, n-butyl sec-butyl, tert-butyl, 2,2-dimethyl-1-propyl, n-pentyl, n-heptyl, n-octyl, chloromethyl, 2-chlorophenyl, 3-chlorophenyl or 4-chlorophenyl.

In particular, the compounds of the invention having excellent activity are those compounds of the general formula I

1) znamenáχ represents a group of formula II

and

Y ₃ and Y ₃ together with

Y ₄ and Y _{5 each} represent an optionally substituted methylene group of the general formula

2) Y ₃ represents a group of the general formula II a

Y ₁ with Y ₂ together and Y ₄ with Y ₅ together are each optionally substituted methylene or

3) Y ₅ represents a group of the formula II and Y f together with Y ₃ together and Y ₃ together with Y ₄ together represent an optionally substituted methylene group. .

The compounds according to the invention are present as optical and optionally also as geometric isomers. The individual isomers and mixtures thereof are also within the scope of the invention.

The compounds of the invention are used either alone or in admixture with one another or with other active ingredients. Depending on the desired objective, means of defoliation, plant protection or pest control may be added.

If it is intended to broaden the spectrum of action, other biocides may also be added. Examples of suitable herbicidally active partners are those mentioned in Weed Abstracts, Vol. 31, No. 7, 1982, entitled "List of Common Names and Abbreviations employed for currently eared herbicides and wild growth regulators in Weed Abstracts".

The active compounds according to the invention or mixtures thereof are expediently used in the form of compositions, such as powders, powders, granules, solutions, emulsions or suspensions, with the addition of liquid and / or solid carriers, diluents and optionally wetting agents, tackifiers, emulsifiers and / or 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, iso. foron, dimethylsulfoxide, dimethylformamide, and oil fractions.

Suitable solid carriers are mineral clays, for example, American fuller's earth, silica gel, talc, kaolin, attaclay, limestone, silicic acid, and plant products such as flours.

Examples of surfactants are calcium ligninsulfonate, polyoxyethylene alkylphenol ether, naphthalenesulfonic acid and its salts, phenolsulfonic acid and its salts, formaldehyde condensation products, aliphatic alcohol sulfonates, and substituted benzenesulfonic acids and their salts.

The proportion of the active compound (s) in the various compositions can vary within wide limits. The composition contains, for example, about 5 to 95% by weight of active ingredient, about 95 to 5% by weight of a liquid or solid carrier, and optionally up to 20% by weight of surfactant.

The use of the composition may be carried out in a conventional manner, for example in water as the carrier in a spraying rate of about 100 to 1000 liters per hectare. The use of the composition in so-called small-volume and ultra-small-volume processes is also possible, as are so-called microgranules.

For example, the following ingredients are used to manufacture the compositions:

A. Dust

a) 40% by weight of the active substance% by weight of clay or clay materials% by weight of colloidal acid 1% · siliceous% by weight of foamed pitch% by weight of a surfactant based on a mixture of ligninsulphonic acid calcium salt with alkylphenol polyglycol ethers

b) 25% by weight of the active substance% by weight of kaolin% by weight of colloidal silicic acid /% by weight of a surfactant based on sodium salt of N-methyl-N-oleyitaurin and calcium salt of lignin sulphonic acid

c) 10% by weight of the active substance% by weight of clay or clay minerals% by weight colloidal silicic acid% by weight foamed pitch% by weight surfactant based on sodium N-methyl-N-oleyltaurine and lignin sulphonic acid calcium

B. Pastes ·% by weight of the active substance% by weight of sodium aluminosilicate% by weight of cetyl polyglycol ether with 8 moles of ethylene oxide% by weight of spindle oil% by weight of polyethylene glycol% by weight of water

C. Emulsion Concentrate

a) 25% by weight of the active substance% by weight of cyclchexanone% by weight of xylene% by weight of a mixture of nonylphenyl polyoxyethylene or calcium dodecylbenzenesulphonate

b) 10% by weight of the active substance% by weight of cyclohexanone% by weight of xylene% by weight of a mixture of noylphenylpolyoxyethylene or calcium dodecylbenzenesulphonate% by weight of a high paraffinic mineral oil.

The novel compounds of the formula I are prepared according to the invention by the preparation of a compound of the formula ΙΓ

CHj — O-Y /

AND

CH_o-Y ₂ '

AND

CH — O — Y3 ‘

AND

CH — O — Y4 ‘

CH2-O-Y ₅ '(II'J wherein one of Y is hydrogen and in each case two of the other substituents Y ' represents a group of the formula ·

R ₂ is reacted with a compound of formula III

where

X represents a halogen atom, preferably a chlorine or bromine atom, optionally in the presence of an acid binding agent and / or a catalyst.

The reaction of the reactants is carried out at a temperature of -10 to 150 ° C, but generally between room temperature and the reflux temperature of the resulting reaction mixture. The reaction time is 1 to 72 hours. The reaction generally proceeds under normal pressure or slight positive pressure. For the synthesis of the compounds according to the invention, the reactants are used in approximately. equimolar amount. A suitable reaction medium is a solvent inert to the reactants.

The choice of solvent or suspending agent depends on the halide and acid acceptor used. Examples of solvents and suspending agents are aliphatic and aromatic hydrocarbons, such as petroleum ether, cyclohexane, hexane, heptane, benzene, toluene, xylene, halogenated hydrocarbons, such as me238397

Т '· ·.

thylene chloride,. ethylene chloride, chlorobenzene, chloroform, carbon tetrachloride, tetrachlorethylene, ethers such as diethyl ether, diisopropyl ether, anisole, dioxane, tetrahydrofuran, carboxylic acid nitriles such as acetonitrile, propionitrile, carboxylic acid amides such as dimethylformamide, dimethylsulfoxide, ketones such as acetone, methyl ethyl ketone, alcohols such as methanol, ethanol, propanol, butanol and mixtures of such solvents with each other. In some cases, the reactant itself may also serve as a solvent.

Suitable acid acceptors are organic bases such as triethylamine, trimethylamine, Ν, Ν-dimethylaniline, pyridine and pyridine bases such as 4-dimethylaminopyridine, or inorganic bases such as alkali metal and alkali metal oxides, hydroxides, carbonates, bicarbonates and alkoxides and alkaline acid salts such as potassium hydroxide, sodium hydroxide, sodium carbonate and sodium acetate.

Liquid bases such as pyridine can be used simultaneously as a solvent. The resulting hydrogen halide can in some cases also be removed from the reaction mixture by purging with an inert gas, for example nitrogen, or absorbed on the molecular network.

The presence of the reaction catalyst may be advantageous. Suitable catalysts are potassium iodide and onium compounds, such as quaternary ammonium, phosphonium and arsonium compounds, as well as sulfonium compounds. Also suitable are polyglycol ethers, especially cyclic ones such as 18-Krown-6, and tertiary amines such as tributylamine. Preferred compounds are quaternary ammonium compounds such as benzyltriethylammonium chloride and tetrabutylammonium bromide.

The compounds produced according to the above process can also be isolated from the reaction mixture in a conventional manner, for example by distilling off the solvent used under normal or reduced pressure, by precipitation with water or by extraction. An increased degree of purity can generally be achieved by column chromatography purification as well as by fractional distillation.

The compounds according to the invention are generally almost colorless liquids which are almost odorless but also partly crystalline. These compounds are sparingly soluble in water, 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 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 dimethyl sulfoxide.

The starting compounds for the preparation of the compounds according to the invention are known per se or can be prepared according to methods known per se. The following examples illustrate the production of the pentitesters of the invention.

Example 1

5-O- [2- (2-Fluoro-4- (4-fluoro-methyl-phenoxy) -2-nitrobenzoyl] -1,2: 3,4-bis-O- (isopropylidene) oxylite

40.0 g (0.172 mol) of 1,2,2,4-bis-O- (isopropylidene-xylite) are added to 250 ml of methylene chloride and 17.3 g (0.172 mol) of triethylamine are added dropwise at 20 ° C. A solution of 65.3 g (0.172 mol) of 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl chloride in 100 ml of methylene chloride was stirred at room temperature for 20 hours.

The reaction mixture is washed three times with 250 ml of water each time. After drying the methylene chloride phase with magnesium sulfate, filtration is performed and the solvent is removed. The remaining oil was digested with 500 ml of hot hexane and then the hexane phase was evaporated again. The recovered oil is dried at 50 [deg.] C. at 1 mbar and then slowly crystallizes.

Yield: 61.2 g (62.4% of theory).

Melting point: 100 to 102 ° C.

TLC: 1: 1 toluene / ethyl acetate.

_Rf value: 0.61.

Analysis:

calculated:

H, 4.37; N, 2.43; Cl, 6.15. Found:

% C, 52.28;% H, 4.27;% N, 2.66.

Other compounds of the invention can be prepared in an analogous manner.

9 ' 10 Physical constant Example Name of the compound 2 1-O- (5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl] -2,3: 4,5-bis- (D-sopropylidene-D-arabite) n _D 2 <>: 1.5067 3 3-O- [5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitrobenzoyl] -1,2: 4,5-bis-O-isoproylidene-adonite n _D 20: 1.5040 4 5-O- (5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-benzoyl] -1,2,4,4-bis-O - [(4-chlorophenyl) methylene] xylite mp: 173 ° C 5 5-O- (5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl) -1,2: 3,4-bis-O- (chloromethylmethylene) xylite n _D 20: 1.5309 6 5-O- [5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl] -1,2: 3,4-bis-O- (methyloctymethylene) xylite 'N _20: 1.4998 7 5-O- [5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl) -1,2: 3,4-bis-O- (ethylmethylmethylene) oxylite n _D 2 ”: 1.5191 8 5-O- (5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl] -1,2: 3,4-bis-O-diethylmethylene) xylite n _D 20: 1.5123 9 5-O- (5-2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl] -1,2: 3,4-bis-O- (methylmethylene) xylite mp: 66-67 ° ^C

The following examples illustrate the possibility of using the compounds of the invention in the form of the formulations mentioned above.

Example 10

In the greenhouse, Viola and Camomile (Matricaria) as plants for pre-emergence and post-emergence testing are sprayed with 3.0 kg of active compound per hectare, emulsified in 500 liters of water per hectare. Three weeks after treatment, the treatment results are evaluated, showing no effect and means destroying the plants.

As can be seen from the table, destruction of the test plants is achieved in general.

12

Compound of the Invention Preemergence Treatment Postemergence treatment

Viola / Matricaria

5-O- [5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl] -1,2,4,4-bis-O- (isopropylidene) xylite 4  ','. 4 4 4 1-O- [5- (2-chloro-4-trifluoromethylphenoxy) - -2-nitrobenzoyl] 2,3: 4,5-bis-O-isopropylidene-D-arabite 4 4 4 4 3-O- [5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl] -1,2: 4,5-bis-O-isopropylidenadonite 4 4 4 4 5-O- [5-2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl] -1,2,4,4-bis-O - [(4-chlorophenyl) methylene] xylite 4 4 4 4 5-O- [5- (2-chloro-4-trifluoromethylphenoxy) -2-nitro-benzoyl] -1,2: 3,4-bis-O- (chloromethylmethylene) xylite 4 4 4 4 5-O- [5- [2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl] -1,2,4,4-bis-O- (methylobtylmethylene) xylite 4 4 4 4 5-O-5- (2-chloro-4-trifluoromethyl-phenoxy) - -2-nitrobenzoyl] -1,2,4,4-bis-O- (ethylmethylmethylene) xylite 4 4 4 4 5-O- [5- (2-chloro-4-trifluoromethylphenyl) -2-nitrobenzoyl] -1,2: 3,4-bis-O- (diethylmethylene) oxylite 4 4 4 4 5-O- [5- (2-chloro-4-trifluoromethylphenoxy) -2-methylbenzoyl] -1,2,4,4-bis-O- (methylmethylene) xylite 4 4 4 4

Example 1 and cl 1 J.

In the greenhouse, after emergence, the plants are treated with the indicated compounds in an amount of 0.1 kg of active compound per hectare. For this purpose, the compound is sprayed evenly onto the plants as an emulsion with 500 liters of water per hectare. Here, 3 weeks after treatment with the compound of the invention, high selectivity and excellent weed control is shown. '

The comparator does not exhibit such an effect. The results are shown in the following table.

A compound of the invention 5-O- [5- (2-chloro-4-trifluoromethyl-phenoxy) -2-nitrobenzoyl) -1,2: 3,4-bis-O- (isopropylidene) xylite 5-O- [5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl) -1,2: 3,4-bis-O- (methyloctylcarbonyl) xylite Comparative composition (according to U.S. Pat. 3 798 276): Sodium 5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoate Matricaria 0 0 2 Polygonům 0 0 0 Viol 0 0 0 Galium 0 '0 1 Centaurea 0 0 1 Aniaranthus 0 0 0 Ipomea 0 0 2 Sesbania 0 0 0 Datura 0 0 0 Abutilon 0 0 3 Soya 10 10 9 Rice 10 10 9 Wheat 10 10 8 Barley 10 10 8 Potato 10 10 9 Underground 1 oil 10 10 10

OBJECT OF THE INVENTION

Claims (11)

A herbicidal composition, characterized in that it contains at least one 5-phenoxybenzoic acid pentite derivative of the general formula I as active substance. CH2-O-Yt CH — O — Y ₂ CH ₂ -O-Y ₂ I ' CH-O-Y4 I ch ₂ -o-y ₃ (I) in which one of the substituents Y represents a group of the formula II and in each case two other substituents Y represent a group wherein Rx is hydrogen or alkyl having 1 or 2 carbon atoms, R ₂ is alkyl having 1-8 carbon atoms, chloromethyl or chlorophenyl. 2. The herbicidal composition of claim 1, wherein the active ingredient is 5-O- (5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl) -1,2: 3,4-bis- O- (isopropylidene) xylite. 3. The herbicidal composition of claim 1, wherein the active ingredient is 1-O- [5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl] -2,3: 4,5-bis- O-Isopropylidene-D-Arabite. 4. The herbicidal composition of claim 1, wherein the active ingredient is 3-O- [5- (2-chloro-4-difluoromethyl-1-phenoxy) -2-nitrobenzoyl] -1,2: 4,5. -bis-O-isopropylidenadonite. 5. The herbicidal composition of claim 1, wherein the active ingredient is 5-O-5- (2-chloro-4-difluoromethylphenoxy) -2-nitrobenzoyl] -1,2: 3,4- bis-O - [(4-chlorophenylmethylene) xylit. 6. The herbicidal composition of claim 1, wherein the active ingredient is 5-O- [5- (2-chloro-4-trifluoromethylphenoxy) -2-nitrobenzoyl] -1,2: 3,4-bis- O- (chloromethylene) xylite. 7. The herbicidal composition of claim 1, wherein the active ingredient is 5-O- [5- (2-chloro-4-difluoromethylphenoxy) -2-nitrobenzoyl] -1,2: 3,4- bis-O- (methyloctylmethylene) xylite. 8. The herbicidal composition of claim 1, wherein the active ingredient is 5-O- [5- (2-chloro-4-trifluoromethylphenoxy) nitrobenzoyl] -1,2: 3,4-bis- O- (ethylmethylene) xylite. 9. The herbicidal composition of claim 1, wherein the active ingredient is 5-O- [5- (2-chloro-4-trifluoromethylphenoxy) -2,2-nitrobenzoyl] -1,2,3,4-bis (ethyl) methylene] xylite. 10. A composition according to claim 1, wherein the active ingredient is 5-O- [5- (2'-chloro-4-trifluoromethyl-phenoxy) [2-nitrobenzoyl] -1,2,3,4-bis (methylmethylene) xylite. . 11. A process according to any one of claims 1 to 10, wherein the compound of formula (II): CH2 —O — Y! * AND CH — O — Y ₂ ' CH — O — Y ₂ ' AND CH — O — Y4 * AND CH.-O-Y, ^-1 (II ') wherein one of Y is hydrogen and in each case two of the other Y' are a group of the formula C / \ R ₂ is reacted with a compound of formula III (LIT) wherein X represents a halogen atom, preferably a chlorine or bromine atom, optionally in the presence of an acid binding agent and / or a catalyst.