FR2649707A1 - OPTICALLY ACTIVE HERBICIDE ACTIVATED (R) -2- (DIBENZOFURAN-3-OXY) -PROPIONIC DERIVATIVES - Google Patents

Abstract

The invention relates to optically active (R) -2- (dibenzofuran-3-oxy) -propionic acid derivatives of formula I (CF DRAWING IN BOPI) in which: Y stands for hydrogen, C1 -C1 4 alkyl , which may be substituted with up to three halogen atoms or with C1 -C4 alkoxy, for C3 -C6 alkenyl, C3 -C6 alkynyl, C3 -C6 cycloalkyl, which may be substituted with methyl or with a residue of formula -N = CR ** 1R ** 2, R ** 1 and R ** 2 representing C1 -C4 alkyl and X stands for fluorine, chlorine, bromine, methyl, ethyl or trifluoromethyl, as well as salts of these compounds. It also relates to a process for their preparation and their use for controlling the growth of undesirable plants.

Description

Substituted dibenzofuran-oxyalkanic acid derivatives in particular

  in position 7 ,, racemic are known as herbicides and are described, for example, in DE-A-2,732,924 and DE-A-2,823,424 as well as in US-4,199,346. indicated as necessary depending on the type of plants targeted - up to 1 kg per ha. It is undoubtedly within the skill of the art to recognize that the compounds described formally must represent racemates and be separable into optical isomers, but no indication of the herbicidal effect of the corresponding antipodes is found.

  It has been found that the (R) -2-acid derivatives

  (Dibenzofuran-3-oxy) -propionic, optically active, defined below and their agronomically compatible salts have a strong unexpected herbicidal effect and are selective with respect to cultivated plants. Their preparation, the means which contain these optically active esters as active ingredients, as well as their use as herbicides, generally and especially for the selective control of weeds in crops of useful plants, such as cereals, are described below. , corn,

rice, sorghum and sugar cane.

  The new derivatives of (R) -2- (dibenzofuran-3-oxy) -

  propionic are defined by the formula I CH3

H-COOY

  Wherein Y is hydrogen, C1-C14 alkyl, which may be substituted by up to three halogen atoms or

  with C1-C4 alkoxy groups for C3-alkenyl

  C6, C3-C6 alkynyl, C3-C6 cycloalkyl, which may be substituted with methyl, or with a residue of

  formula -N = CR1R2, R1 and R2 representing C1-alkyl

  C4 and X is for fluorine, chlorine, bromine, methyl, ethyl or

trifluoromethyl.

  (R) -2- (dibenzofuran-3-oxy) acid derivatives

  Propionic compounds of formula I are extraordinarily suitable for the control of broadleaf weeds, such as, for example, Abutilon theophrasti, Amaranthus retroflexus, Asclepias spp., Chenopodium album-, Chrysanthemum segetum, Datura stramonium, Euphorbia geniculata, Galium aparine, Ipomoea spp., Matricaria chamomilla, Nicandra physaloides, Polygonum persicaria, Sesbania exaltata, Sinapis arvensis, Solanum nigrum, Stellaria media, Viola tricolor, Mentha arvensis and Xanthium pensylvanicum, in the most diverse agricultural monocot crops.

  (R) -2- (dibenzofuran-3-oxy) acid derivatives

  propionic of formula I and their salts have in the pre- and post-emergence process an excellent herbicidal effect. The active ingredients have an unparalleled selectivity that extends to a few field crops, such as cereals (barley, wheat, oats), maize, rice, sorghum and sugar cane. What is surprising is that the herbicidal effect of the optically active derivative is, at half use dose, stronger than that of the corresponding racemate. The alkyl residues for Y in formula I can be branched or unbranched and have 1 to 14 carbon atoms. Residues of 1 to 8 carbon atoms are preferred, especially methyl, i-pentyl, n-octyl, i-octyl, 2-ethyl-n-hexyl. Examples of halogen-substituted alkyl radicals are, in particular,

  alkyl residues substituted with chlorine, such as 2-

  chloro-ethyl, 4-chloro-n-butyl, 2,2,2-trichloro-

  ethyl. Examples of substituted alkyl radicals

  alkoxy are methoxymethyl, 2-methoxy-ethyl, 2-ethoxy-

  ethyl, 2-n-butoxyethyl. Preferred alkenyl, alkynyl and cycloalkyl radicals are allyl, propargyl, cyclohexyl, 2-methylcyclohexyl. As representatives of the group -N = CR1R2 are to be considered in particular the

residues -N = C (CH3) 2 and -N = C (C2H5) 2.

  Preferred substituents for X in formula I are

chlorine and bromine.

  The compounds of formula I are obtained by reacting at a sufficient temperature, below 120 degrees C, a corresponding dibenzofuran-3-ol of general formula with the corresponding S-enantiomer of a propionic acid ester of formula III CH

Z-CH-COOY

* (III)

  Wherein Z is chlorine, bromine, mesylate or trosylate, in the presence of an acid acceptor, such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate. and, inter alia, in the presence of a diluent, such as, for example, water, methanol, ethanol, propanol, isopropanol, acetone, acetonitrile, dioxane, dimethylformamide, or mixtures thereof. If the optically active R-propionic acid derivative of formula IV CH 3 is available

EH -CO OH (LV)

  it is of course also possible to react with the corresponding alcohol YOH (V) under conditions

standard esterification.

  When reacting a dibenzofuran-3-ol of formula II with an ester of formula III, a Walden inversion takes place on the chiral carbon atom of the ester

  propionic acid. This has the consequence that

  enantiomer of the propionic ester (III), the Renantiomer of the ester (I) or

the acid of formula IV.

  The esterification of the acid (IV) with the alcohol (V) is

  unfolds with maintenance of the configuration.

Examples of preparation

Example 1

  R - (+) - 2- (7-chlorodibenzofuran-3-oxy) -propionic acid 54.6 g (0.25 moles) of 7-chlorodibenzofuran-3-ol in ml of ethanol are added, dropwise dropwise, g (0.75 mole) of 50% sodium hydroxide solution. Then 54.6 g (0.4 mole) of ethyl S - (-) - chloropropionate are added dropwise over a period of 30 minutes at 50 ° C. and 70 mbar. A mixture of ethanol and water is distilled off. After ml of distillate, 100 ml of water are added, the mixture is stirred for min at 100 ° C. and under normal pressure, the mixture is cooled to 20 ° C. and 500 ml of water are added.

  and acidified with concentrated hydrochloric acid.

  The precipitate is separated by spinning, washed with water and

  dried. 71 g (97.8% of theory) of R-acid are obtained.

  (+) - 2- (7-Chlorodibenzofuran-3-oxy) propionic acid

  of gray-white crystals with a melting point of 178-

  degrees C and [] D, acetone = + 61.7 degrees C.

Example 2

  R - (+) - 2- (7-chloro-dibenzofuran-3-oxy) -propionate n

octyl

  A mixture of 14.5 g (0.05 mol) of R - (+) - 2- (7-

  chlorodibenzofuran-3-oxy) -propionic acid, 13 g (0.1 mol) of n-octanol, 75 ml of cyclohexane, 75 ml of toluene and 0.5 g of toluenesulfonic acid are stirred under reflux until 0 9 g of water is separated. The mixture is cooled to 20 degrees C, washed with water, dried over Na2SO4 and concentrated under reduced pressure. We obtain

  19 g (94.4% of theory) of R - (+) - 2- (7-

  N-octyl chlorodibenzofuran-3-oxy) propionate

  white crystals with a melting point of 36-

  37.degree. C. and 1.10.degree. C. acetone = 67.1.degree. C. In a similar manner, according to Preparation Examples 1 and 2, the compounds of formula I are obtained, which are indicated in Table 1. provide, because of their similar structural characteristics, an effect similar to that of the compounds indicated in.

the synthesis examples.

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Table 1

CH3

0-CH-COOY

  X (I) Principle. Active Actlf X - pf [] DAceton [OC]

3 F H 177-179 +70.9

4 Br H 155-158 +56.80

5.CH3 H +66.20

6 C2H5 H -62.1

7 CF3 H -58.30

8 Cl-CH3 87 +69.9

9 C1 -C2H5 59-61 +72.8

  ## STR1 ## n-C5H11 26- 28 +750 Cl-CH2-CH2CH (CH3) 2 oil +72.30 16 Cl n-C6H13 oil +70.4 17 Cl Cyclohexylc. oil +76.9 18 Ci-CH3-CH (CH3) -CH2) 5-CH3 oil +63, 90 19 Cl-CH2-CH (C2H5) (CH2) 3-CH3 oil +68.40 Ci n-C9H1g oil +68.9 21 Ci n-C1OH21 oil +68, 4 22 Ci n-C14H29 43-45 +49.9

  23 C1-CH2-CH2-O-CH2CH3 '43-45 +60.8

  C1-CH2-CH2-O- (CH2) 3-CH3 oil +55.6 Ci-CH2-CH2-Cl oil +66.20 26 Cl - (CH2) 4-Cl oil +66.0 27 Ci-CH2 -CCl3 oil 28 Br -CH3 77-79 + 5 &, 8 29 Br -C2H5 63-65 +56.7 Br n-C3H7 62-64 +56.80 31Br i-C3H7 97-99 +56, 9 32 Br 59-61 +56.70 33 Br S-C4Hg 69-72 +56.8 Table 1 (continued) Principle Pf E [] D, Acetone Active [oc] Ne 34 Br -CH2-CH2-CH (CH3 ) 2 oil + 56.80 Br n-C6H13 oil +56.90 36 Br Cyclohexyl, 92-94 +57.00 37 Br -CH2CH (C2H5) -CH2) 3CH3 oil +56.5

38 CF3 -CH3

39 CF3 -C2H5

CF3 S-C4H9

41 CF3 n-C6H13

42 CF3-CH2-CH (C2H5) - (CH2) 3CH3

43 CF3 -CH2-CH2-0-CH3

44 CH3 - -CH3

CH3-CH2-CH (C2H5) - (CH2) 3CH3

46 C2H5 n-C4H9g 47 C2H5 S-C4-Hg

C2H5-CH2-CH (C2H5) - (CH2) 3CH3

9--

  Derivatives of (R) -2- (dibenzofuran-3-ox) acid -

  Propionic I or the herbicidal agents containing them can be used for example in the form of directly sprayable solutions, powders, suspensions, even aqueous suspensions or other high percentage of the oil, or dispersions, emulsions, dispersions in the oil, pulp, solid spreading products, granules, spraying, fogging, dusting, spreading or watering. The forms of application depend entirely on the purpose of use. In any case, they must ensure the finest possible distribution of the principles

active agents according to the invention.

  To prepare directly sprayable solutions, emulsions, pastes or dispersions in the oil, mineral oil fractions having medium to high boiling points, for example kerosene or gas oil, can be used. coal tar oils, etc., as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example benzene,

  toluene, xylene, paraffin, tetrahydro-

  naphthalene, alkylated naphthalenes, or derivatives thereof, for example methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents for example dimethylformamide, dymethylsulfoxide,

N-methylpyrrolidone, water.

  Aqueous use forms are prepared by adding water to emulsifiable concentrates, wettable pastes or powders, dispersions in the oil. To prepare emulsions, pastes or dispersions in the oil, the substrates can be homogenized as such or dissolved in an oil or a solvent, with wetting agents, adhesives, dispersants or emulsifiers in water. . Concentrates for further dilution into water from the active ingredient can also be prepared with wetting agents, dispersants, adhesives or emulsifiers, or optionally solvents or oil. Surfactants include: the alkaline, alkaline-earth and ammonium salts of lignin sulfonic acid, naphthalenesulfonic acids, phenolsulphonic acids, alkylaryl sulfonates, alkyl sulfates, sulfonates, and the like. alkyl, salts

  alkaline and alkaline-earth salts of dibutyl

  naphthalenesulfonic acid, lauryl ether sulphate, fatty alcohol sulphates, alkaline or alkaline-earth fatty acid salts, hexadecanol, heptadecanol, sulphated octadecanol salts, sulfated fatty alcohol glycol ether, condensation products of naphthalene sulfonated and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene-octylphenol ether, isooctylphenol ,

  octylphenol, ethoxylated nonylphenol, polyglycol

  alkylphenol tributylphenyl ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol and ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol acetal and polyglycol ether, sorbite esters, lignin, sulphite waste liquors, and methylcellulose. The powders, the solid spreading products, the dusting powders are obtained by mixing or grinding the active ingredients together with a powder.

solid support.

  The granules are obtained, for example by coating, impregnation or direct coating, by fixing the active ingredients on solid supports. Solid supports are, for example, mineral soils, such as silica gel, silicic acids, silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bowl, loess, clay, dolomite, diatomite, calcium and magnesium sulphate, magnesium oxide, crushed plastics, fertilizers, eg ammonium sulphate, ammonium phosphate, nitrate ammonium, urea and vegetable products, for example cereal flours, bark powder from trees, wood, or nut shells,

  cellulose and other solid supports.

  The compositions contain between 0.1 and 95% by weight of active material, preferably between 0.5 and 90% by weight. Examples of formulations are given below: 20 parts by weight of the compound N. 19 are dissolved in a mixture of 80 parts by weight of xylene, parts by weight of the adduct of 8 to 10

  moles of ethylene oxide to 1 mole of N-

  oleic acid monoethanolamide, 5 parts

  weight of the calcium salt of dodecylbenzene

  sulfonic acid and 5 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. Pouring the solution into 000 parts by weight of water and finely distributing therein, an aqueous dispersion is obtained containing 0.02% by weight of active ingredient. 20 parts by weight of the compound N. 19 are dissolved in a mixture of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide on 1 mole of isooctylphenol and parts by weight of the adduct of 40 moles of ethylene oxide on 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it, an aqueous dispersion containing 0.02% by weight is obtained.

weight of active ingredient.

  III. 20 parts by weight of compound 8 are dissolved in a mixture of 25 parts by weight of cyclohexanol, parts by weight of a fraction of mineral oil having a boiling range of between 210 ° C. and 280 ° C. 10 parts by weight of the adduct of 40 moles of ethylene oxide with 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it, an aqueous dispersion containing 0.02% by weight is obtained.

weight of active ingredient.

  IV 20 parts by weight of the compound N. 2 are suitably mixed with 3 parts by weight of the salt

  sodium of diisobutylnaphthalene acid-

  sulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulphite waste liquor, and 60 parts by weight of pulverulent silica gel, after which it is milled in a hammer mill. By distributing the mixture finely in 20,000 parts by weight of water, a spray mixture containing 0.1% by weight is obtained.

weight of active ingredient.

  V 3 parts by weight of the compound N. are intimately mixed with 97 parts by weight of finely divided kaolin. We get a porduit to powder

  containing 3% by weight of active ingredient.

  VI 30 parts by weight of the compound N. 8 are intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil, previously sprayed onto the surface of the silica gel. This gives a preparation of active principle of good adhesiveness. VII 20 parts of the compound N. 19 are intimately mixed with 2 parts of the calcium salt of the acid

  dodecylbenzene sulphonic acid, 8 parts of fatty alcohol

  polyethylene glycol ethyl ether 2 parts of the sodium salt of a phelolsulfonic acid / urea / formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. We hold

a stable oily dispersion.

  The application can be carried out by treatment in pre-

  emergence or post-emergence. In the case where the active ingredients are less well tolerated by certain cultivated plants, it is also possible to use application techniques with which the jet of the products, by means of the sprayers, is oriented in such a way that the leaves of the cultivated plants sensitive are the least achievable as active ingredients arrive on the leaves of undesirable plants growing below or on the surface

  soil not covered with vegetation (post-directed,

  by). Depending on the time, the target plants and the stage of development, the doses of active ingredient use range from 0.001 to 3 kg / ha, preferably from 0.01 to

0.1 kg / ha.

  To broaden the spectrum of activity and achieve synergistic effects, the new substituted cyclohexenone derivatives can be applied alone as well as mixed and applied with many participants from other groups of herbicidal or growth regulating active ingredients. For example, as partners for mixtures, diazines, derivatives of 4H-3,1-benzoxazines, benzothiadiazinones,

  2,6-dinitroanilines, N-phenylcarbamates, thiol

  carbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils,

  benzofuran derivatives, quinolino acid derivatives

  carboxylic derivatives, cyclohexan-1,3-dione derivatives, phenoxy- and heteroaryloxy-phenoxypropionic acids, and

  as their salts, esters, amides and others.

  In addition, it may be useful to apply cyclohexenone derivatives of formula I or herbicides containing them alone or mixed in combination with other herbicides or other plant protection agents, for example with the control means. against pesticides or fungi or bacteria

  plant pathogens. It is also interesting to mix

  with mineral salt solutions that are incorporated to compensate for nutrient or micronutrient deficiency. You can also add oils or

  non-phytotoxic oily concentrates.

  Considering the possible spectrum of activity by the control of weeds, the compatibility for the cultivated plants or the undesirable influence on the growth of these plants and taking into account the very varied methods of application, the compounds according to the invention, can be used for a large number of

of cultivated plants.

  Examples include: Botanical name French name Avena sativa oat Pennisetum glaucum millet candle (penicillary) Saccharum officinarum sugar cane Secale cereal rye Sorghum bicolor common sorghum Sorghum dochna sweet sorghum Triticum aestivum soft wheat Triticum durum durum wheat Triticale Zea mays but

  as well as turf grass and fodder.

  EXAMPLE OF APPLICATION The herbicidal effect on the growth of test plants

  (R) -2- (dibenzofuran-3-oxy) -propionic acid derivatives

  Formula I is demonstrated by greenhouse trials.

  As culture vessels, plastic flower pots with a content of 300 cm 3, filled with clay sand at about 3% humus as substrate are used. The seeds of the plants to be studied are sown

  shallow, separately depending on the species.

  For the post-emergence treatment plants seeded directly or in the containers and grown in them are selected, or seedlings are transplanted into the test vessels a few days before the planting. treatment. The test plants, according to their growth form, are grown to a height of 3 to 15 cm and then treated by suspending or emulsifying them in water as a dispersant and sprayed. through nozzles ensuring a fine division. The application rates are 1.0 kg / ha. in

post-emergence treatment.

  The test vessels are installed in a greenhouse by selecting rather warm places (20 to 35 degrees C) for heat-loving species and temperatures of 10 to 20 degrees C for those from climates

  temperate. The trial period is 2 to 4 weeks.

  During this time the plants are cured and their reaction on the different treatments is evaluated. It is evaluated on a scale from 0 to 100. 100 y means: no emergence of the plants or complete destruction of the aerial parts at least and O means

  no damage or normal growth course.

  The plants used for greenhouse trials belong to the following types: Galium aparine (cleavers) GALAP Nicandra physaloides NICPH Sinapis alba (white mustard) SINAL Solanum nigrum (black morel) SOLNI Abutilon theophrastii (Chinese jute) ABUTH Polygonum persicaria (lady's knotweed) ) POLEP -17- As comparison agents were tested the racemates of dibenzofuranoxide derivatives

CH3 (A; DE-A 28 23 424)

ICF COOCH3

CIJO

-. CH3

  COOCH-H (CH 2) 3 -CH 3 (B, DE-A 28 23 424)

Ci 2H5 CH3

H-COOCH3

(C; DE-A 28 23 424)

  The results are shown in Tables 2 & 4.

Table 2

  Ex.N. Application Rate Test Plants and Damage (%) [kg / ha] GALAP NICPH SINAL

8 0.060 85 75 80

^ 0.125 80 65 70

Table 3

  Ex.N. Application Rate Test Plants and Damage (%) [kg / ha] GALAP NICPH

  ________________________________________________________

19 0.125 80 70

B 0.250 65 70

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Table 4

  Ex.N. kg a.S./ha Test plants and damage (%)

ABUTH GALAP POLPE

28 0.03 80 95 -

0.06 85 94 65

0.125 90 94 95

0.25 95 93 95

C 0.125 45 70 -

0.25 80 65 40

0.5 82 72 60

1.0 100 73 60

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Claims (5)

claims   1. (R) -2- (dibenzofuran-3-oxy) acid derivatives   Optically active propionic acid of formula I H3 0-CH-COOY (I)   wherein Y is hydrogen, C1-C14 alkyl, which may be substituted by up to three halogen atoms or   with C1-C4 alkoxy groups, with C3-alkenyl   C6, C3-C6 alkynyl, C3-C6 cycloalkyl, which may be substituted by methyl or by a residue of formula -N = CR1R2, R1 and R2 representing C1-C4 alkyl and X is fluorine, chlorine, bromine; methyl, ethyl or trifluoromethyl   as well as the salts of these compounds.   2. Process for preparing (R) -2-acid derivatives   (Dibenzofuran-3-oxy) -propionic compound of the formula I according to Claim 1, characterized in that a corresponding dibenzofuran-3-ol of the general formula II x (II) is reacted at a temperature which is sufficient, less than degrees C. ) with the corresponding S-enantiomer of a propionic acid ester of formula III-CH3 Z-CH-COOY (III)   in which Z is used for chlorine, bromine, mesylate or trosylate, in the presence of an acid acceptor and a diluent, or an optically active (R) propionic acid derivative of formula IV CH3 XHCOOH (IV)   (IV) with the corresponding alcohol YOH (V) under conditions standard esterification.   3. Herbicidal Agent Containing a (R) -2-Acid Derivative   (dibenzofuran-3-oxy) -propionic compound of formula I according to   claim 1, or a salt of such a derivative.   4. A herbicidal agent containing inert additives and a (R) -2- (dibenzofuran-3-oxy) -propionic acid derivative of formula I according to claim 1, or a salt thereof. 5. A method of controlling the growth of undesirable plants, characterized by the fact that the plants and / or their biotope act in an effective amount   from the herbicidal point of view of an acid derivative (R) -2-   (dibenzofuran-3-oxy) -propionic compound of formula I according to   claim 1, or a salt of such a derivative.