PL101303B1 - A weedicidal and phytohormonal agent - Google Patents

Description

The subject of the invention is a herbicide and phytohormonal agent which contains as active ingredients at least one 1,2,4-oxadiazinone-5 derivative of general formula 1.

In this formula, the symbol R represents a hydrogen atom or an alkyl radical containing 1: -4 hydrogen atoms or a phenyl radical, Ar is a phenyl radical substituted with 1-3 identical or different substituents, which can be halogen atoms and alkyl radicals containing 1-4 carbon atoms, a hydroxyl group, alkoxy groups in which the alkyl radical contains 1-4 carbon atoms, alkylthio in which the alkyl radical they contain 1-4 carbon atoms, alkylsulfinyl in which the alkyl radical contains 1-4 carbon atoms, nylon in which the alkyl radical contains 1-4 carbon atoms, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, carboxylic, alkoxycarbonyl with an alkyl part containing 1-4 carbon atoms, nitro, amine, allylamino with the alkyl part containing 1-4 carbon atoms, dialkylamino in which each alkyl radical contains 1-4 carbon atoms, acylamino radicals in which the acyl moiety contains 1- ^ l atoms carbon, alkoxycarbonylamino in which the alkyl radical contains 1-4 carbon atoms, azide, alkanoyl containing 1-4 carbon atoms, sulfamoyl, dialkylsulfamoyl in which each alkyl radical contains 1-4 carbon atoms or. a phenyl radical or an aromatic heterocyclic radical of 5 members which as the heteroatom contains an oxygen, sulfur, or nitrogen atom, optionally substituted with a selected atom or radical among halogen atoms, alkyl radicals containing 1-4 carbon atoms, phenylalkyl radicals in which the alkyl part contains carbon atoms, alkoxy atoms in which the alkyl part contains 1-4 atoms carbon or alkylthio in which the alkyl moiety contains 1-4 carbon atoms.

New compounds of general formula 1 can be prepared by cyclization of a compound of general formula 2, and where Ar and R are defined as above and R! is an alkyl radical having 1-4 carbon atoms.

Cyclization is usually carried out by heating in an alkaline environment. Especially ko it is preferable to carry out the reaction in an organic solvent, e.g. pyridine, or also an alcohol such as e.g. ethanol in the presence of an alkali metal alkoxide, such as sodium methyl or ethyl 2 101 303 Compounds with general formula 2 can be obtained by either of the following methods: A) Action of an a-haloester of general formula 3, where R and Rj are defined as above and Y represents a halogen atom on an amidoxime of general formula in which Ar is as defined above. Reactions is performed mostly in an aqueous organic solvent such as a mixture of ethanol and water or dimethylformamide and water in the presence of a basic condensing agent such as hydroxide to sodium, potassium hydroxide or tetralkylammonium hydroxide and at a temperature between 20 and 80 ° C.

In some cases, this reaction can directly yield a cyclic compound of formula I without passing through an intermediate of formula 2. Compounds of general formula 4 can be obtained by action hydroxylamines onto nitriles of general formula Ar-CN in which Ar is as defined above. Reactions are performed mostly in an organic solvent such as aqueous ethanol at temperature between 20 and 80 ° C.

B) The action of the α-aminooxyester of the general formula 5, where R and Rx are defined as above, on the salt iminoether of the general formula 6 in which Ar is as previously defined and HA is an acid molecule hydrochloric (HCl) or fluorobic acid (BF4H). The reactions are usually carried out in a basic solution in an organic solvent such as pyridine at a temperature of about 20 ° C.

A salt of the iminoether of the general formula 6 can be obtained by treatment with an ethanolic solution of hydrochloric acid on the nitrile of the general formula Ar-CN or by the action of triethyloxonium fluoroborate (Merwein salt) on the amide of general formula Ar-CONH2 in which Ar is as defined above.

C) Action of the compound of general formula 2 on the compound of formula RtOH, in these formulas Ar, R and Ri are as defined above. The reactions are carried out by heating the compound of formula 7 in the presence of an alcohol of formula RjOH.

According to the invention, the new compounds of the general formula I can also be obtained by an α-amino treatment of the oxyester of general formula 5 to the salt of the iminoether of general formula 6, the reactions being carried out in a basic organic solvent, such as pyridine, under reflux (method B).

New compounds of general formula 1 can also be obtained by treating a compound of general formula 8 (where R and Ar are as defined above and X is halogen, preferably chlorine or bromine) an aqueous alkali metal hydroxide solution (Method C).

Compounds of general formula 8 can be obtained by treatment with an acid chloride of general formula 9, wherein R and X are defined as above, on the aminoxime of general formula 4.

The reactions are mostly performed in an organic solvent such as dioxane and toluene in the present carry pyridine.

New compounds of general formula 1 can possibly be purified by physicochemical methods such as like crystallization or chromatography. Compounds according to general formula 1 show remarkable properties, which makes them especially useful in the field of agriculture.

If they are used in doses of 1 to 100 g / hl of water, then they show particularly interesting properties. phytohormonal benefits. In this case, they have an auxinic effect analogous to that of indole acid acetic acid or phenoxyacetic acid derivatives. They are mainly useful for improving fruiting certain plants (tomatoes), preventing leaf or fruit fall, or finally improving rooting plants.

The compounds of formula I, when used in doses from 0.5 to 5 kg / ha, show herbicidal properties, especially against dicotyledonous plants, both in pre-emergence and post-emergence applications.

The composition according to the invention contains at least one compound of the general formula I as active ingredient in combination with a carrier and / or surfactant, and optionally one or more agents auxiliary substances compatible with the active substance or substances and used in agriculture.

These preparations may contain other pesticides, such as fungicides or insecticides.

The active ingredient content in these preparations may be from 0.105 to 95% by weight.

The term "carrier" as used herein means an organic or inorganic natural substance or synthetic, which is combined with the active ingredient to facilitate its application to plants, grains or soil either for transport or handling. The carrier can be a solid (clays, silicates natural or synthetic, resins, layers, solid fats) or liquid (water, alcohols, ketones, petroleum fractions, chlorinated hydrocarbons, liquefied gases).

The surfactant may be an emulsifying, dispersing or wetting agent where each can be ionic or non-ionic. Mention may be made, for example, of the salts of polyacrylic acids, acid lignin sulphonates, condensation products of ethylene oxide with fatty alcohols, fatty acids or fatty amines. 101 303 3 The preparations according to the invention may be produced in the form of wettable powders, dusting powders nations, granules, solutions, emulsifiable concentrates, emulsions, suspension concentrates and aerosols.

Wettable powders are usually prepared at a content of 20-95% by weight of active ingredient and in addition solid carrier from 0 to 5% wetting agent, from 3 to 10% by weight of dispersant and if necessary from 0 to 10% by weight of a stabilizer or stabilizers and / or other additives such as penetrating agents, binders or anti-sticking agents, dyes, etc.

Dusts are usually produced in the form of a dust concentrate with a composition similar to that of wettable powder composition or without dispersing agent. At the place of use, they are diluted with additional amount of solid carrier in such a way as to obtain a preparation containing usually from 0.5 to 10% by weight of active ingredient. Typically, the emulsifiable concentrates used for spraying contain in addition to solvent and, if required additional solvent, from 10 to 50% by weight (by volume of the substance) active content, from 2 to 20% by weight) by volume of emulsifiers and from 0 to 20% by weight (volumetric suitable additives such as stabilizers, corrosion inhibitors, penetrating agents, barium penetrations and binders. The suspension concentrates, also used for spraying, are prepared so as to obtain mac persistent liquid substances do not settle. They usually contain from 10 to 75% by weight of the substance active, from 0.5 to 15% by weight of surfactants, from 0.1 to 10% by weight of surfactants against sedimentation such as protective colloids and thixotropic agents from 0 to 10% by weight of suitable additives such as foaming agents, corrosion inhibitors, stabilizers, penetrating and binding agents and as a water carrier or an organic liquid in which the active substance is insoluble.

Some organic solids or mineral salts can be dissolved in the medium to prevent it sedimentation or as antigels to water.

The general scope of the invention also includes aqueous suspensions and emulsions, for example preparations obtained by dilution * with water of a wettable powder or an emulsifiable concentrate. These emulsions may be of the type "Water-in-oil" or of the "oil-in-water" type and may have a thick consistency such as, e.g., Mayonnaise.

For the so-called "very small volume" application method of spraying into very fine droplets, solutions are prepared in organic solvents containing from 70 to 99% of the active substance.

The formulations according to the invention may contain other ingredients, such as, for example, protective colloids, agents adhesion promoters or thickeners, thixotropic agents, stabilizers, binders as well as other known active substances with pesticidal properties, especially insecticides or fungi deadly.

As an example, the composition of a wettable powder is given, the percentage being expressed by weight.

Active substance 50% Calcium lignin sulfonate (stabilizer), 5% Isopropylnaphthalene sulfonate (wetting agent) 1% Silica caking agent. .. .- ••• '$% Filler (kaolin) 39% The following non-limiting examples illustrate the preparation of compounds which may be used to be used in the composition according to the invention.

Example I. Method B. 47.8 g of ethyl 4-chlorobenzimidazoleate hydrochloride, 34 g of hydrochloride Ethyl aminooxyacetate and 820 ml of anhydrous pyridine are heated under reflux for 16 hours with stirring.

The pyridine is evaporated under reduced pressure (20 mm Hg) and then the concentrate is treated with 600 ml ethyl acetate and 300 ml of water.

The organic phase is decanted and then washed three times with 100 ml of water. After drying over With anhydrous sodium sulfate, the solvent was evaporated under reduced pressure (20 mm Hg).

The solid residue is treated with 100 ml of isopropyl ether and the crystals are separated by filtration. Received 24.1 g of 3 < 4-chlorophenyl) -5,6-dihydro (4H) -1,2,4-oxadiazinone-5 are found.

After recrystallization from 7 parts by volume of ethanol, the product has a melting point of 170 ° C.

The ethyl 4-chlorobenzimidazole hydrochloride used as the starting compound can be prepared according to L. Weintraub, S. R. 01esa and N. Kalisha, J, Org.Chem. 33, 7679 (1963).

Example II. The procedure is as in example I but starts with 2-chlorobenzi-hydrochloride ethyl midazolate and ethyl aminooxyacetate hydrochloride to give 80% yield of 3 <2-chlorophene nyl> 5,6-dihydro (4H) -1,2,4-oxadiazinone-5 with a melting point of 132 ° C, Examples III-VI. Proceeding as in example I and proceeding from the appropriate exemption relationships the following products are obtained: 4 101 303 1 Example no III IV V VI Ar 1 ' Formula 10 Formula 11 Formula 12 Formula 13 R H. H. H. H. Performance 66%. 63% 58% 67% Temperature melting after recrystallized licking 251 212 179 128 Example VII. Method A. 14.1 g of O-ethoxycarbonylmethyl- (5-chlorothiophene) -carboxyainidoxime-2 and 2.9 g of dry sodium methylate in 140 ml of ethanol are stirred for 3 hours at room temperature.

The ethanol is evaporated off under reduced pressure and then the solid residue is treated with 100 ml of water distilled. The solution thus obtained is acidified by adding 54 ml of normal hydrochloric acid. Establishment- The white, white crystals are separated by filtration and then washed with water. After drying you get , 7 g of 3- (5-chloro-2-thienyl / dihydro / 4H) -1,2,4-oxadiazinone-5, m.p. 210 ° C.

Examples VIII-XXXI. By following example VII and starting with the appropriate relationships the following products are obtained from the output: Example no VIII IX X Xl XII XIII XIV XV XVI XVII XVIII XIX XX XXI XXII Xxiii Xxiv Xxv XXVI XXVII Xxviii XXIX xxx XXXI Ar no Formula 14 Formula 14 Formula 15 Formula 16 Formula 17 Formula 18 Pattern 19 Formula 20 Pattern 21 Pattern 22 Pattern 23 Pattern 24 Pattern 25 Pattern 26 Pattern 27 Pattern 28 Pattern 29 Pattern 30 Pattern 31 Pattern 32 Pattern 33 Pattern 34 Pattern 35 Pattern 36 R H. ¦CH3 H. H. H. H. H. H. H. H. H. H. H. H. H. H. H. H. H. H. H. H. H. H. Performance 72% 87% 96% 77% 9071. 92% ' 69% 91% 89% 89% 81% 90% 84% 73% 81% 68% 76% 71% 81% 93% 64% 76% 97% 77% Temperature melting after • recrystallized licking 180 187 183 186 210 215 143 261 100 127 210 210 146 184 130 203 148 126 190 164 132 203 123 Example of phen "describes the preparation of 3- (2-thienyl) -5,6-dihydrogen (4H) -1,2,4-oxa- diazinon-5 by the method of C. Tenze, the compound has already been described in example VIII only then to be obtained Method A was applied to the solution. 1.42 g of thiophenecarboxamidoxime-2 in 20 ml of dioxane are added dropwise 1.13 g of chloroacetyl chloride within 10 minutes. 101 303 5 The resulting white precipitate is dissolved by adding 3 ml of pyridine to the reaction mixture. After elapsed 16 hours at 20 ° C a brown oil separates. The solvents are evaporated off at temperature around 20 ° C under reduced pressure (40 mm Hg then 1 mm Hg) and then the residue is treated ml of water. The resulting precipitate is filtered off and washed twice with 5 ml of water. After draining, it is replaced 1.1 g of O-chloroacetylthiophenecarboxamidoxime-2 melting at 156 ° C are added. 1 g of O-chloroacetylthiophenecarboxamide oxim-2 is dissolved in 20 ml of toluene and heated to reflux for reflux within 16 hours. After decolorization with animal carbon, the solution is concentrated to a decrease at a pressure of 20 mm Hg, and the precipitated crystals were dried under reduced pressure (1 mm Hg) at around 20 ° C. 0.9 g of 5-chloromethyl-3-2-thienyl) -1-t4-oxadiazole is obtained, melting at temperature 57 ° C. 0.67 g 5 5 ml of an aqueous 2N sodium hydroxide solution are added to the solution obtained, and the mixture is stirred for 30 minutes.

It is then acidified with 0.9 ml of 2N hydrochloric acid, the crystals obtained are filtered off and washed 4 times 10 ml of water each. After drying, 0.46 g of 3β2-thienyl) -5,6-dihydrogen (4H) -1,4-oxo dia- zinon-5, melting at 180 ° C.

Example XXXIII. The compound described in this example was prepared according to a variant of Process A in the following manner yielding directly the reaction of the α-haloester of general formula 3 with an amidoxime of general formula 4. In this the case of indirect compound 2 was not identified and there was a simultaneous reaction of compound 3 with it cyclization of the resulting compound.

28.4 g of thiophenecarboxamidoxime-2 are added to 200 ml of ethanolic 2N sodium hydroxide solution. and then within 30 minutes a solution of ethyl α-bromobutyrate in 200 ml of ethanol. The reaction mixture is stirred for 16 hours and then distilled the alcohol at a temperature of about 25 ° C under reduced pressure (20 mm Hg). The residue obtained is treated with 200 ml of water and 100 ml of ether and then decanted and washed the organic phase with 100 ml of water.

The aqueous solutions are combined and acidified with 14 g of citric acid. A precipitate is obtained that drained and washed three times with 20 ml of water, and then dried at a temperature of about 20 ° C under reduced pressure (1 mm Hg).

10.38 g of 6-ethyl-3- 2-thienyl) -5,6-dihydrogen (4H) -1,2,4-okA-5-adiazinone-5 are obtained. at 171 ° C. After recrystallization from acetonitrile, the melting point of the pure compound is 176 ° C.

Example XXXIV Following as in Example XXXIII and starting with 20 g of thiophene carboxamide xime-2 and 34.2 g of ethyl α-bromophenylacetate, 10.3 g of 6-phenyto-3- (2-thicnyl) -5,6-dihydrogen- (4H) - are obtained 1,2,4-oxadiazinone-5 which melts after recrystallization at 173 ° C.

Example XXXV. For a solution of 25 parts of 3 "(2-thienyl) -5,6-dihydro-1,2,4-oxadiazinone-5 10 parts of the product are added in 65 parts of a mixture of equal parts of toluene and acetofcnon condensation of ethylene oxide and octylphenol in the ratio of 10 molecules of ethylene oxide per 1 molecule of octylphenol nolu. The solution is suitable for use after diluting with water in the proportion of 10 ml of solution per 100 liters of water.

The phytohormonal activity of the compounds according to the invention can be demonstrated by the following tests: a) Fruiting of tomatoes. 1 drop is placed on a bunch of thinned tomatoes (0.05 ml) of the solution or suspension of the compound to be tested. After an observation period of 15 days the percentage of fruit formed, relative to the control, is recorded. At a concentration of 100 mg / liter, the relation to the amount of clade VIII shows 100% fruiting compared to the control (0%). Fruits formed they are grainless. b) Planting tomato leaves. The third and fourth leaves are taken from the stems of tomatoes (Mar- mande) with 5-6 leaves. The petiole of each leaf is dipped to a depth of 2-3 in the test tube. 8 days after the start of the test, the number of roots formed is measured and counted on the petioles of the treated leaves. At a concentration of 10 mg / l, the compound of Example VIII gives 100% production the root cause of the leaves, while 0% rooting is found on the petioles of the control plants.

The herbicidal activity of the compounds of general formula I can be seen as follows: Grains of various plant species (wheat; Triticum satfrum, lentils; Lens culinaris, radish; Raphanus sativus, sugar beet; Beta yulgaris and grasshopper; Alopecurus agrestis) is sown at the bottom plastic cups with a capacity of 180 ml containing a complex mixture at a height of 6 cm with: 1/3 clean soil, 1/3 humus and 1/3 river sand: About 30 grains are placed in each pot.

For each compound concentration, 2 pots of wheat and 4 pots of other species are used. To post-emergence treatment, grain is sown in the greenhouse one week before the start of the trial so as to young plants were at the time of treatment in the following stages of development: wheat and fowl in the 2-3 leaves, lentils at the 3-leaf true leaf stage, beetroot and radish at the 2-leaf well developed stage. 101 303 Treatment is carried out by spraying a solution or suspension of the compound and the pots are placed on the rotary device. Each pot receives 1 ml of solution. The doses of the test compound are 1 and S kg / ha.

During the pre-emergence test, the surfaces of the pots with sown seeds are dried and then covered I am the same mixture of soil at a height of 1 cm. The pots are watered twice a day by sprinkling.

In a post-emergence test, the treated plants are left dry.

The earthen mixture is moistened by placing the pots in a flat vessel containing water. In two in cases, the pots are placed in a greenhouse (temperature 22-24 ° C, relative humidity 70-80%) at artificial lighting of 5000-6000 lux at plant level and illuminates them daily for the next 17 hours. After 3 weeks of treatment, the number of plants in each pot is counted and measured their height. The results are given as a percentage of the control. The results are summarized in the table below.

Claims (2)

Patent claims a1 | rf | f% w # i / ywiaia ^ y 1 A. ilnmv wrulnm liih radical Ft% nvlnwv Ar fi7ti9C7ji rndnilr fftrnrlfMW nfiH «fjiwtanv 1 * \ I ¦L-tj | L | ¦mMjT.UiB.ii luft * / Awv% rwm!% Ma / 1 • # • wattlranii lrttf% * i / mi ulam Hi / ó mttwwm s * hlfimu // * ai rsw1 * tilri • 11r «1tf \ tu * 9 «U /« Ara «« s »A | : j ^ alrturtf - "jJ. ——-— - L-_j | yjL ^ jl.1 g% mmrm unitw -IL-j-LL-gmrlfYuj *. ¦¦ »lrlAwf /« tl m / lnilr allralrtufi / fiuiura 1 A al / \ rrk «r wfint cnina alKflotio in whose source aiiciiowv contains 1-4 atoms. aiKilosullinvJowa. Which radical ^ ILUjfcii * 9 * u * l ** «i jj **>% *» ¦% / nf ^ itlm allrtlrtAilfrtrii / Irtuji w trt / \ r * ir / irlnilr allrilmra Tflis / iAra i> j otrtmi / w * al a trifluoromethyl, trifluoromethoxy, trinoroinethylthio, carboxyl, alkoxycarbonyl with a part in which the acyl part contains 1-4 carbon atoms, alkoxycarbonylamino in which the alkyl radical contains 1. A. afrttwy wAffln s7vdkows fllkunotlown 72tW4 £ Rtiac: i 1—4 iitoniv u / fiftla sulfamoyl dwiialkyl sulfdmooyl in irlAr »i IrslfHf mrfrttlr ullfil / twt / Tiftu / tAra l uh * tAr * 0 milliv l uh * nvlowv fllhft arnmalvr7nv rrwlnilfphprocyclic with 5 members, which, as hetereoatom, contains an oxygen, sulfur or nitrogen atom, optionally substituted with an atom or a radical selected from halogen atoms, alkyl radicals containing 1-4 carbon atoms, phenylalkyl radicals containing 1 -4 alkyl alkyl radicals , alkoxy groups in which the alkyl moiety contains 1-4 carbon atoms or alkylthio in which the C1-6alkyl group contains 1-4 carbon atoms, and a carrier and / or a surfactant suitable for use in agriculture. 2. The measure according to claim .1, characterized in that it contains an active ingredient of 0.005-95% by weight. q \ 101 303 7 8? PT i 3 § 3 h- * tr ° o 1 »-» ooo 1 ° to o 1 ^ o 1 K »o 00 o 1 00 1 <-n OOOO ¦ ^ O 1 - ^ 1 1 ^ o this oooo this o X oo 00 ooooo 1 oooooo -p * o LU ooooooo X oo »- * oooo 8 to ooo IM o -o \ J \ oo -o O i _ ooooo N> ooo 1 <1> - <1 t— (oo AD o 8 oooo Ol o vO Ol oo vO o ^ oooooooo 1 k— <o Ol oo to oi o 5 oo -J oo Os oooooo 1 h "~ '00 u— oo - 00 00'" "'00 - 00 * ~ ^ oo - 00 ^ 1 00? - »1 oo 1 ¦-o 1 CA N a> B. wo N CD 2 o '8 <5 * i ^ p? r 3 o N 3 * 0 P o & 3 oo oo N ot 1 o * td 6 * pso 1 o 1 PLN Hi • * - Before 1 * * £ §: ^ * 2 & 3 C £> 3 'o 3 <N oo ou plant' ha101 303 0 R. 0 ^ NN ' i H MODEL 1 Y-CH-C00R IR MODEL 3 N-OH Ar - C \ \ NH Ar - CR yN - OCH - COORj MODEL ARHM - 0-CH-COOR 2 1 MODEL 2 MODEL 5 Ar - C NH 0-CH 2 5 H ~ A X-CH- IR -CN 0 MODEL 6 MODEL 8 Ar - C / R NO-CH-COCL 'NH • HCL X-CH - COCL i R MODEL 9 MODEL 7101 303 // ^ _ oh MODEL 10 OCH 3 PATTERN 11 CL CL -o- PATTERN 17 PATTERN 18 CH- IJ PATTERN 19, S PATTERN 14 -o PATTERN 14 S "PATTERN 12 -d 3 PATTERN 13 PATTERN 16 MODEL 15 OHIN tQ MODEL 20 £ ^> CH3 chI ^ i 3 MODEL 21 N Sv MODEL 22101 303 ~ QN (CH3) NC> * \ _ - / ^ MODEL 26 / CL MODEL 27 -CFc CL MODEL 26 / F ('¦ W 3'2 PATTERN 23 WZ (3R 29 -O PATTERN 24 PATTERN 30 ~ ^ -S0N (CH) 2 "**" "¦ ¦ / 3 2 PATTERN 25 ^ -v— OH -O PATTERN 31 S0oN (CH) 2 3 2 DESIGN 32 9 SO NH 2 2 NO MODEL 33? W SCF 3 STYLE 34i 01 .MU S02CH3 STYLE 35 r STYLE 36