GB2181133A

GB2181133A - Herbicidal phenoxy benzoyl malonates

Info

Publication number: GB2181133A
Application number: GB08623486A
Authority: GB
Inventors: Tamas Komives; Ferenc Dutka; Istvan Barta; Istvan Jablonkai; Agnes Hulesch; Ferenc Bihari; Gyula Eifert; Peter Bohus; Mihaly Nagy; Mihaly Barabas; Istvan Kuronya
Original assignee: Budapesti Vegyimuevek Rt; Magyar Tudomanyos Akademia Kozponti Kemiai Kutato Intezet
Current assignee: Budapesti Vegyimuevek Rt; Magyar Tudomanyos Akademia Kozponti Kemiai Kutato Intezet
Priority date: 1985-10-01
Filing date: 1986-09-30
Publication date: 1987-04-15
Also published as: IL79974A0; NL8602481A; DE3632492A1; DD255729A5; JPS6281353A; CS273620B2; HU196884B; SE8604148D0; GB8623486D0; CS705886A2; FR2587998B1; AU595834B2; SE8604148L; GB2181133B; HUT41590A; CH676595A5; DD249840A5; AU6326686A; BE905534A; IL79974A

Description

1 GB 2 181 133A 1

SPECIFICATION

Herbicidal phenoxy benzoyl malonates This invention relates to herbicidal phenoxy benzoyl malonates, a process for the preparation 5 thereof, herbicidal compositions comprising the same and a method for combating weeds by using the said compositions.

It is known that certain phenoxy benzoic acid derivatives possess herbicidal effect. Such compounds are disclosed in US patent specifications Nos. 3 979 437 and 3 652 645.

According to an aspect of the present invention there are provided new phenoxy benzoyl 10 malonates of the general Formula 1 0 A 5 0 C-OR R2, C CH 5 -R 4 C-OR 0 9 ,R3 @. 0 (I) (wherein R' stands for halogen, cyano, nitro, methylthio, trifluoromethyl or C,4 alkyl; R2 and R3may be the same or different and represent hydrogen, halogen or trifluoromethyl; R4 stands for hydrogen, halogen, cyano or nitro and R5 represents C,-4 alkyl which may be same or different).

The new compounds of the general Formula 1 differ from the known derivatives in the structure of the moiety atached to the carbonyl group.

The new compounds of the general Formula 1 exhibit a significantly stronger herbicidal ef fect-particularly pre-emergent herbicidal effect-than the chemically related known derivatives.

The compounds of the present invention are particularly preferable when used in pre-emergent 30 application for the selective control of grassy and broad-leaved weeds in various cultures, particularly in maize.

In a preferred sub-group of the compounds of the general Formula 1 R, is chlorine or trifluoro methyl, R2 represents chlorine, R3 stands for hydrogen or chlorine, R4 is nitro, halogen or cyano and 115 stands for ethyl.

Preferred compounds of the general Formula 1 are those in which R, stands for trifluoromethyl, R2 represents chlorine, R3 is hydrogen, R 4 stands for nitro and R5 is ethyl.

Another preferred group are those compounds of the general Formula 1 in which R' is trifluoromethyl, R 2 and R3 stand for chlorine, R 4 represents nitro, and Rr' is ethyl.

A further preferred group are those compounds of the general Formula 1 in which R, and R2 40 are chlorine, R3 is hydrogen, R4 stands for nitro and R5 is ethyl.

The term "C,-, alkyl- relates to straight or branched chained alkyl groups having 1-4 carbon atoms (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl etc.).

According to a further aspect of the present invention there are provided herbicidal compo sitions comprising as active ingredient 0.01-95% by weight of a compound of the general 45 Formula 1 (wherein W, R 2, R4 and R5 are as stated above) in admixture with suitable inert solid and/or liquid carriers or diluents and optionally auxiliary agents (e.g. surfactants, antifoam, antifreezing and adhesive agents etc.).

The compositions of the present invention may be solid or liquid and may be finished in usual forms (e.g. powder mixture, dusting powder, granule, paste, emulsion, suspension, solution, 50 spray, concentrate etc.). The compositions comprise diluents and carriers and auxiliary agents generally used in agriculture and plant protection.

The solid carriers may be mineral or synthetic materials e.g. China-clay, siliceous earth, talc, attapulgite, diatomaceous earth, alumina, silicic acid and various silicates. As liquid diluent e.g.

mineral oil fractions (e.g. gas oil or Kerosine), oils of animal or vegetable origin; aromatic, aliphatic or alicyclic hydrocarbons (e.g. benzene, toluene, xylene, cyclohexane, tetrahydro na phthalene etc.) and derivatives thereof (e.g. chloro benzene, alkyl naphthalenes, cyclohexanol, butanot etc.) or strongly polar solvents (e.g. dimethyl formamide, dimethyl sulfoxide, N-methyl pyrrolidone, water etc.) may be used.

The surfactants (emulsifying, dispersing, wetting, antifoam or antiaggregating agents) may be 60 of ionic or non-ionic character. As ionic surfactants the following compounds may be used: salts of saturated or unsaturated carboxylic acids; suifonates of aliphatic, aromatic or aliphatic-aromatic hydrocarbons, sulfonates of alkyl, aryl and aralkyl alcohols; suffonates of alky], aryl and aralkyl alcohols; sulfonates of alkyl, aryl and aralkyl carboxylic acids and esters and ethers thereof; sulfonates of condensation plauds of phenols, cresols or naphthalene; sulfatated oils of animal or 2 GB 2 181 133A 2 vegetable origin; alkyl, aryl or aralkyl phosphate esters; sulfonates and phosphates of polyglycol ethers of ethylene oxide formed with fatty alcohols or alkyl phenols.

As non-ionic surfactants e.g. the following compounds may be used: condensation products of ethylene oxide formed with fatty alcohols; alkyl aryl polyglycol ethers; polymers of ethylene oxide andlor propylene oxide and derivatives thereof; alkyl cellulose.

As antifoam agents e.g. ethylene oxidelpropylene oxide condensation products having a 1 ' ow molecular weight; aliphatic alcohols; special silicon oils or fatty acid amides may be used.

As adhesive or thickening agent e.g. alkaline earth metal soaps; salts of sulfosuccinic acid esters; or macromolecular natural or synthetic macromolecular materials which are soluble or swellable in water may be used.

As antifreezing agent e.g. ethylene glycol, propylene glycol or glycerol may be used.

The herbicidal compositions of the present invention may be prepared by known methods of pesticidal industry by admixing at least one compound of the general Formula 1 with suitable inert solid and/or liquid carriers or diluents and optionally with auxiliary agents.

According to a still further aspect of the present invention there is provided a method for 15 controlling weeds which comprises applying onto the objects to be protected-preferably onto plants, parts of plants or soil-an effective amount of a compound of the general Formula 1 or a composition comprising the same.

According to a still further aspect of the present invention there is provided a process for the preparation of compounds of the general Formula 1 (wherein R', R2, F13, R4 and R5 are as stated 20 above) which comprises a) reacting a phenoxy benzoic acid derivative of the general Formula 11 0 2 1 25 R C-Y Ri- 0- R 4 R3 (wherein W, R, 113 and 114 are as stated in the preamble and Y represents halogen, cyano or C,6 alkyl-carbonyloxy) with a metal derivative of a malonate of the general Formula Ill 0 M_ 5 35 C OR CHj G I IJI --, C-OR5 11 0 a (wherein R5 is as stated in the preamble) or in the presence of a metal compound-preferably 45 magnesium chloride-with a malonate of the general Formula 111; or b) reacting a phenol of the general Formula IV R2 50 R1 OH CV) 'R 3 -6 (wherein W, R2 and R3 are as stated in the preamble) or an alkali metal salt thereof with a 55 benzoic acid derivative of the general Formula V 0 0 9 5 1 1 C-OR C-CH 11.1 5 60 4 C-OP Z_ R A - (V g- 0 (wherein R4 and R5 are as stated in the preamble and Z represents halogen).

3 GB 2 181 133A 3 According to process a) it is preferred to use a sodium, potassium or magnesium derivative of the malonate of the general Formula Ill. If the malonic acid derivative of the general Formula Ill is used per se it is preferred to carry out the reaction in the presence of magnesium compound particularly magnesium chloride as metal compound. The reaction may be carried out preferably in an inert solvent. As solvent advantageously a hydrocarbon (e.g. benzene, toluene or xylene), an ether (e.g. diethyl ether, 1,2-dimethoxy ethane, tetrahydrofuran or dioxan) an amide (e.g. dimethyl formamide, hexamethyl phosphoric acid triamidd) a ketone (e.g. acetone or diethyl ketone) or a nitrile (e.g. acetonitrile) etc. may be used.

The malonic acid derivatives of the general Formula Ill are reacted in the form of a metal salt thereof with the compound of the general Formula 11. The metal salts of the malonates may be 10 prepared previously e.g. by reacting a malonate of the general Formula Ill with an alkali or alkaline earth metal compound or a metal organic compound. According to an other alternative the reaction of the compounds of the general Formula 11 and Ill is carried out in the presence of a metal compound-preferably magnesium chloride. In this case the metal salt of the malonate of the general Formula 111 is formed in situ in the reaction mixture.

The reaction may be accomplished at a temperature between - 1 O'C and + 18WC, preferably at 30-100"C. The desired compound is separated by known methods after the removal of the by-products formed.

The malonates of the general Formula Ill and metal salts thereof and the starting materials of the general Formula 11 are partly known compounds. Such compounds are disclosed in US patent 20 specifications Nos. 3,979,437 and 3,652,645 and in the publications Org. Synth. Coil. Vol. 285 and J.Org. Chem. 50, 2622 (1985). The new compounds of the general Formula 11 may be prepared in an analoguous manner to the process described in the said publications.

According to process b) the compounds of the general Formulae W and V are reacted preferably in the presence of an inert solvent or diluent. As reaction medium the solvents disclosed above in connection with process a) may be used. It is preferred to work in the presence of an acid binding agent e. g. an alkali hydroxide, alkali carbonate, alkali ethylate or alkali tert. butylate or any suitable organic base (e.g. triethyl amine).

Further details of the present invention are to be found in the following Examples without limiting the scope of protection to the said Examples.

Example 1

Preparation of diethyl-5-(2-chloro-4-trifluoromethyl-phenoxy)-2nitrobenzoyl-malonate a) To a solution of 38.0 9 of 5-(2-chloro-4-trifluoromethyi-phenoxy)-2- nitro-benzoy1 chloride and 50 mi of benzene an ethoxy magnesium malonate solution prepared from 17,6 9 of diethyl 35 malonate in 50 m] of benzene is added at room temperature under stirring within 20 minutes.

The addition having been completed the reaction mixture is refluxed for an hour and thereafter cooled. To the viscous solution 50 m] of 20% sulfuric acid are added under stirring. The phases are separated and the aqueous layer is extracted twice with 50 mi of benzene each. The united extracts are washed with water and a sodium hydrogen carbonate solution whereupon the solvent is distilled off. The residual yellow oil becomes slowly crystalline. This 47.8 g of the desired compound are obtained, mp.: 72-76'C.

b) A mixture of 19.7 9 of 2-chloro-4-trifluoromethyl-phenol, 32,7 9 of diethyi-2-nitro-4-fluoro benzoyl-malonate and 100 mi of anhydrous dimethyl sulfoxide is stirred at 5WC. After a reaction time of 24 hours the reaction mixture is diluted with 100 mi of water and extracted three times 45 with 50 mi of benzene each. The benzene phase is dried over magnesium sulfate and the solvent is distilled off. The residual yellow oil is recrystallized from a mixture of benzene and hexane. Thus 40.3 g of the desired compound are obtained, mp.: 72-76'C.

c) A mixture of 21.9 9 of sodium-2-chloro-4-trifluoromethyl-phenolate, 32. 7 g of diethyl-2 nitro-4-fluoro-benzoyi-malonate and 100 mi of anhydrous dimethyl sulfoxide is stirred at WC for 50 24 hours. The reaction mixture is diluted with 100 m] of water and extracted three times with mi of benzene each. The benzene phase is dried over magnesium sulfate and the solvent is distilled off. The residual yellow oil is recrystallized from a mixture of benzene and hexane. Thus 39.8 g of the desired compound are obtained, mp.: 72-76'C.

Example 2

Preparation of diethyl-5-(2,6-dichloro-4-trifluoromethyl-phenoxy)-2-nitrobenzoyl-malonate To a solution of 45.8 9 of 5-(2,6-dichloro-4-trifluoromethyi-phenoxy)-2- nitro-benzoyl bromide in mi of ether a diethyl potassium malonate solution prepared from 17.6 9 of diethyl malonate in 50 mi of ether is added dropwise under stirring at room temperature within 20 minutes. The 60 addition having been completed the reaction mixture is refluxed for an hour, cooled and 50 mi of 20% sulfuric acid are added under stirring. The phases are separated, the aqueous layer is extracted twice with 50 mi of ether each. The organic solutions are united, washed successively with water and a sodium hydrogen carbonate solution and the solvent is removed. The residual yellow oil slowly solidifies. Thus 49,9 9 of the desired compound are obtained, mp.: 84-88'C. 65 4 GB 2 181 133A 4 Example 3 Preparation of diethyl-5-(2-chforo-4-trifluoromethyl-phenoxy)-2- chloro-benzoyi-malonate To a mixture of 35.0 g of 5-(2-chloro-4trifluoromethyi-phenoxy)-2-chloro-benzoic, and 10.1 9 5 of triethyl amine formed in 100 mi of toluene and cooled to O'C with salted ice 12.1 g of pivaloyl chloride are added at a rate that the temperature should not exceed O'C. During the addition and the subsequent stirring period (15-20 minutes) triethyl amine hydrochloride precipi tates. The dropping funnel of pivaloyl chloride is replaced by a dropping funnel containing an ethoxy magnesium malonate solution prepared from 17.6 g of diethyl malonate. During the dropwise addition of the ether solution the temperature is kept at a value between -WC and 10 O'C. The reaction mixture is allowed to stand overnight whereupon 200 mi of a 5% sulfuric acid solution are added. The aqueous phase is extracted twice with 50 mi of ether each. The united organic extracts are washed with diluted sulfuric acid and a sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate and evaporated. 44.3 g of the desired compound are obtained in the form of slightly yellowish crystals, mp.: 59-65'C.

Example 4

Preparation of diethyl-5-(2,4,6-trichforo-phenoxy)-2-nitro-benzoylmalonate Into a 500 mi flask equipped with a stirrer and a dropping funnel 9.52 9 of anhydrous magnesium chloride and 100 mi of anhydrous acetonitrile are introduced. To the heterogenous 20 mixture 16.2 g of diethyl malonate are added. The flask is placed into an ice bath and 28 mi of triethyl amine are added. To the solution at WC 38.1 g of 5-(2,4,6trichloro-phenoxy)-2-nitro- benzoyl chloride are added dropwise under stirring within 15 minutes. The reaction mixture is stirred at O'C for an hour and at room temperature for 12 hours, cooled to WC, whereupon 60 mi of a 5 M hydrochloric acid solution are added. The solution formed is extracted three times 25 with 100 m] of ether each, the united extracts are dried over magnesium sulfate and the solvent and the traces of diethyl malonate are removed. The residual slightly yellowish oil slowly solidifies. Thus 45.0 9 of the desired compound are obtained, mp.: 71-73C.

Example 5

The following 19 compounds of the general Formula 1 enumerated in Table 1 are prepared in an analoguous manner to the preceding Examples. In the said Table 1 the definition of symbols W-Rs, the melting points and the characteristic data of the NIVIR spectra are disclosed.

1 Table 1

Compound 1 2 3 4 5 O.P. 1 No. R R R R R ( 0 c) h - N 14 R 0PM) 1 W 3 cl H NO 2 c 2 H 5 72-76 1.10 (m, CH3) 4. 1 CH 2) 4.93 (s, CH); 7.6 (m, ar-11) 2. CF3 cl Cl NO 2 c 2 H 5 84-88 1.0 (m, CH 3); 4.3 CH 2); 5.0 (s, Cli); 8. 0 (in, ar-H) 3. CF 3 Cl H cl c 2 H 5 59-65 1. 1 (in, CH3); 4.0 (in, CH 2); 4.7 (s, CH); 7.6 (m, ar-H) 4. cl cl cl 140 2 c 2 H 5 71-73 1.0 (m, CH 3); 4.0 (m 1 CH 2); 4,95 (s, CH); 7.9 (m, ar-H) 5. cl Cl H NO 2 c 2 H 5 62-65 1.15 (m, qH,) 4.1 (in, CH 2) 4.90 (s, C0; 7. 7 (m, ar-H) 6. CF3 Cl H CN c 2 H 5 87-93 1.1 (in, CH 3 4.0 (in, Cif 2) 4.85 (s, CH); 7.7 (m, ar-11) 7. CF 3 F H H c 2 H 5 ' oil 1.0 em ' CH 3 4.0 (in, CII 2) 4.8 (S, C11); 7. 8 (m, ar-11) 8. CF3 H F NO 2 c 2 H 5 47-49 1.0 (in, CH 3); 4.1 (in, CH 2) 4.9 (s, CH); 7.8 (m, ar-H) 9. CH H Cl Br C H oil 0.95 (m, CH,); 4.0 (in, CH 4.8 Cs, CH); '(.'f (m, ar-11) 3 2 5.> 2 10. CF 3 H Cl NO 2 CH3 oil 3.67 (s, CH3?; 4.8 (s, CH); 7.8 (in, ar-H) 11. N02 Cl H NO 2 c 2 H 5 oil 1.05 (m, CH. 4.1 (in, CH 2 4.87 (5, Cl-1); 7.6 (m, ar-H) 12. CN cl H cl c 2 H 5 oil 1.10 (m, CH 3 4.0 (in, CH 2 4.7 (s, Cif); 7.6 (ni, ar-li? 13. CH 3 S Cl H Cl CH3 oil 3.7 (in, CH31 CH3S); 4.8 Cs, CH); 7.3 (m, ar- H) 14. cl CF 3 H 1,10 2 c 2 H 5 67-71 1.10 (M, CH:;); 4.0 (in, C1'd 4.80 (s, Cif); 7.65 (m, ar-H) 15. C17 3 H cl N02 CH 3 oil 3.71 (in, OCH3); 1.02 (in, CCH 3); 3.95 (in, CH 2 4. 31 (s, CH? c 3 H 7 7.6 (in, Ar-11) cl (71 6 GB2181133A 6 Preparation of herbicidal compositions Example 6

Granules having an active ingredient content of 0.01% 2.3 9 of technical grade compound No. 1 (purity: 89%) are dissolved in 97. 7 8 of methylene 5 chloride to yield a solution having a concentration of 2% by weight. An acidic pearl siliceous earth carrier prepared from 4000 g of diatomaceous earth are placed into a Loedige 20 type turbine stirrer; the average particle size of the carrier is between 0.5 and 2 mm. 20 9 of the active ingredient premix (2% mm/m solution) are sprayed onto the granulated carrier through Tee-Jet 10080 nozzles at a rate of 5 g/minutes, whereby the granules are stirred in the Loedige 10 type stirrer with a velocity of 50 r.p.m. The sorption type granules are packed.

Example 7 Sprayable powder having an active ingredient of 95% 15 240 g of compound No. 2 (purity 97%) previously powdered in a mill equipped with a rotating 15 blade are admixed with 2.5 g of Cab-O-Sil M5 (amorphous silica; carrier) and 7.5 g of type 1494 dispersing agent (sodium salt of the condensation product of suifonated cresole and formaldehyde) in a mortar. The powdered mixture is ground in a turbine mill (Alpine LIVIRS80) under an injected airpressure of 5 bar and a grinding air pressure of 4.5 bar at a feeding rate of 20 250 g/h. Although the sprayable powder thus obtained contains no separate wetting agent it is 20 readily wettable, and has a maximal particle size of 20 urn. In a spray having a concentration of 10 911 the floatability at 30'C after 30 minutes is as follows: 84% in CIPAC standard D water; and 91% in CIPAC standard A water.

Example 8

Emulsifiable concentrate having an active ingredient content of 24% g of Tween 85 (Trade Mark) (ethoxylated sorbitane trioleate) and 30 g of Sapogenat T (ethoxylated tributyl phenol) emulsifiers and 250 9 of technical grade compound No. 7 (purity: 96%) are dissolved in 400 g of cyclohexanone at 40-45'C under stirring. When all the 30 components are dissolved the solution of the active ingredient (temperature 40-45'C) is poured into a mixture of 200 g of ionexchanged water and 70 g of ethylene glycol under vigorous stirring whereupon the mixture is cooled to 15-20'C. Before the termination of the stirring period 10 9 of Silicon S RE antifoam agent (a 30% emulsion of dimethyl silicon oil) are added to the emulsion and five minutes later the stirring is stopped.

Example 9 Biological application of the composition Grass seeds and seeds of cultivated plants are sown into sand of the river Danube in plastic boxes (size loxioxio cm) and compositions prepared from the emulsifiable concentrates of the test compounds are sprayed onto the surface of the sand (pre-emergent treatment) and three weeks after sowing (post-emergent treatment). The plastic boxes are watered at a rate required for normal plant growth and are kept in a glass house. The results of the treatment are evaluated after a test period of four weeks and assessed with the aid of a scale from 0 to 10, wherein O=no symptoms and 10=completely destroyed infected plants (100%).

As reference compounds two commercially available herbicides are used, namely acifluorfen [chemical name: sodium-5-(2-chloro-4-trifluoromethyi-phenoxy)-2-nitro- benzoate] and oxifluorfen [chemical name: 2-chloro-l-(3-ethoxy-4-nitro-phenoxy)-4-trifluoromethyI benzene].

The results are summarized in Table 11. It appears from the said data that the activity of the compounds of the present-as the average activity against grassy and broad leaved weeds-is 50 superior to that of the reference compounds, particularly in pre-emergent application.

The tolerance of a number of cultivated plants against the compositions of the present invention has been determined by means of the treating methods disclosed in this Example. It has been found that dicotyledonous cultivated plants tolerate well the compositions of the present invention and in the herbicidal dose none of the invention compounds cause any phytotoxic symptoms. It has also been found that while in pre-emergent treatment maize, sunflower and leguminous plants tolerate well the invention compounds, only soya tolerates oxifluorfen and acifluorfen used as reference compounds.

1 Table II

Herbicidal activity of the compounds of the general Formula 1 against various weeds in several cultivated_plant cultures in pre-emergent and post -eme rgent treatment Test compound Dose kg Amaranthus Chenopodium Echinochloa Setaria soya pea maize sun flower No. active retroflexus album crus-galli italica ingredient/ha pre post pre post pre post pre post pre post pre post pre post pre 3.

1. 0.3 6 6 6 8 6 5 6 5 0 0 0 0 0 4 0 6 1.0 9 8 9 10 8 9 10 10 0 2 1 6 1 8 2 10 2. 0.3 6 6 6 8 6 5 6 5 0 0 0 0 0 4 0 6 1.0 9 8 9 10 8 9 10 10 0 2 1 6 0 8 2 10 0.3 5 4 5 5 4 4 4 4 0 0 0 0 0 4 0 6 1.0 8 5 8 6 6 6 8 6 0 2 1 3 0 6 0 a 4. 0.3 9 8 8 8 6 5 6. 5 0 0 0 2 0 4 0 6 1.0 10 10 10 10 10 10 10 10 1 2 1 6 1 8 2 8 5. 0.3 9 8 8 9 7 5 6 5 0 0 0 2 0 4 0 6 1.0 10 10 10 10 10 10 10 10 1 2 1 6 1 8 2 8 6. 0.3 6 6 6 6 6 4 4 5 0 0 0 2 0 3 0 6 1.0 8 7 8 7 8 6 8 6 0 2 1 6 0 6 0 8 7. 0.3 6 4 6 4 6 4 5 5 0 0 0 2 0 3 0 6 1.0 8 5 8 5 8 6 8 6 0 2 1 6 0 6 0 8 8.

0.3 4 4 6 4 6 4 5 5 0 0 0 2 0 3 0 6 1.0 6 6 8 6 8 6 8 6 0 2 1 6 0 6 0 8 0.3 4 4 4 4 7 4 5 5 0 0 0 2 0 3 0 6 1.0 6 5 6 5 8 6 8 6 1 2 1 6 0 6 0 8 post G) CD N) 00 W W OD (Continuation of Table II) Test compound Dose kg Amaranthus Chenopodium Echinochloa Setaria soya pea maize sun flower No. active retroflexus album crus-galli italica ingredient/ha pre post pre post pre post pre post pre post pre post pre post pre post 10. 0.3 8 10 6 10 8 8 8 8 0 0 0 2 0 4 0 6 1.0 10 10 9 10 10 10 10 10 1 2 1 7 2 8 2 10 11. 0.3 6 4 6 6 7 6 6 5 0 0 0 0 0 4 0 5 1.0 8 5 7 8 8 7 10 8 0 2 1 6 1 6 2 10 12. 0.3 6 4 5 6 8 6 7 5 0 0 0 0 0 3 1 6 1.0 7 5 7 8 10 10 8 6 0 1 1 5 1 6 2 8 13. 0.3 4 4 4 4 5 5 5 5 0 0 0 0 0 3 0 5 1.0 7 6 6 5 8 6 8 6 1 2 1 3 1 5 1 6 14. 0.3 6 5 7 6 7 6 8 7 0 0 0 0 0 4 0 6 1.0 8 6 8 7 9 8 10 10 0 2 1 6 1 8 0 a 15. 0.3 6 7 6 7 6 6 5 6 0 0 0 0 0 4 0 6 1.0 8 9 10 9 9 9 10 10 0 2 1 6 1 8 2 10 acifluorfen 0.3 6 7 5 7 8 6 8 7 3 0 4 2 6 4 6 6 re fe re nce 1.0 8 10 8 10 8 9 10 10 6 2 8 7 8 8 10 10 oxifluorfen 0.3 6 6 6 6 6 8 6 7 3 0 4 3 6 4 6 6 reference 1.0 8 10 8 10 8 10 10 10 6 3 9 8 8 9 10 10 1, 1 1.'.

a) W N) 00 W W CO 9 GB 2 181 133A 9

Claims

CLAIMS 1. Phenoxy-benzoyl-malonates of the general Formula 1

0 0 A A C-ORS C - CH R -CC -0- -R 4 C-OR (I) 0 H R 3 51 0 (wherein R' stands for halogen, cyano, nitro, methylthio, trifluromethyl or C,-, alkyl; R2 and R3 may be the same or different and represent hydrogen, halogen or trifluoromethyl; 15 R4 stands for hydrogen, halogen, cyano or nitro and R5 represents C1-4 alkyl which may be same or different).
2. Compound according to Claim 1 wherein R' stands for trifluoromethyl, R2 represents chlorine, R3 is hydrogen, R4 stands for nitro and R5 is ethyl.
3. Compound according to Claim 1 wherein R' is trifluoromethyl, R2 and R3 stand for chlorine, 20 R4 represents nitro and R5 is ethyl.
4. Compound according to Claim 1 wherein R' and R2 are chlorine, R3 is hydrogen, 114 stands for nitro and R5 is ethyl.
5. Herbicidal composition comprising as active ingredient in an amount of 0.01-95% by weight a phenoxy-benzoyl malonate of the general Formula 1 0 1 5 0 C-OR 1 1.1 R2, C - CH "% al- 4 C-OR CC)- 6. 0 (wherein R' stands for halogen, cyano, nitro, methylthio, trifluromethyl or C,-4 alkyl; R2 and 113 may be the same or different and represent hydrogen, halogen or trifluromethyl; R4 stands for hydrogen, halogen, cyano or nitro and R5 represents C,-4 alkyl which may be same or different) in admixture with suitable solid and/or liquid carriers-preferably silicic acid, silicon dioxide and/or cyclohexanone-and optionally auxiliary agents-preferably surfactants, such as ethoxy- 40 fated tributyl phenol or an alkyl sulfonate.
6. Herbicidal composition according to Claim 5 comprising as active ingredient a compound of the general Formula 1 wherein R' stands for trifluoromethyl, R2 represents chlorine, R3 is hydrogen R4 stands for nitro and R5 is ethyl.
7. Herbicidal composition according to Claim 5 comprising as active ingredient a compound 45 of the general Formula nitro and R5 is ethyl.
8. Herbicidal composition according to Claim 5 comprising as active ingredient a compound of the general Formula 1 wherein R' and R2 are chlorine, R3 is hydrogen, R4 stands for nitro and R' is ethyl.
9. Process for the preparation of phenoxy-benzoyl malonates of the general Formula 1 1 wherein R' is trifluoromethyl, R 2 and R3 stand for chlorine, R4 represents 0 1 5 0 C-OR 1 1.1 C -- CH 0 4 C-OR 0 (I) (wherein R' stands for halogen, cyano, nitro, methylthio, trifluoromethyl or C,-4 alkyl; 112 and R3 may be the same or different and represent hydrogen, halogen or trifluoromethyl; 65 GB2181133A 10 R4 stands for hydrogen, halogen, cyano or nitro and R5 represents Cl-4 alkyl which may be same or different), which comprises a) reacting a phenoxy benzoic acid derivative of the general Formula 11 0 R2 1 - Ri- 0 0- 4 @ 3 R (11) (wherein W, R2, R3 and R4 are as stated in the premable and Y represents halogen, cyano or C,-, alkyl-carbonyloxy) with a metal derivative of a malonate of the general Formula Ill 0 0- 5 C OR CHj 1 41 (111) 20 C-OR5 11 0 t (wherein R5 is as stated in the premable) or in the presence of a metal compound-preferably magnesium chloride-with a malonate of the general Formula 111; or b) reacting a phenol of the general Formula IV 30 R2 R (M 35 (wherein W, R2 and 113 are as stated in the preamble) or an alkali metal salt thereof with a benzoic acid derivative of the general Formula V 0 40 0 1 1 C-OR OO,C-CH,-.C-ORS Z-@-R 4 1 (V 0 45 (wherein R4 and R5 are as stated in the preamble and Z represents halogen).
10. Process for the preparation of phenoxy-benzoyl malonates of the general Formula 1 (wherein R' stands for halogen, cyano, nitro, methylthio or trifluromethyl or C,4 alkyl; R2 and R3 may be the same or different and represent hydrogen, halogen or trifluoromethyl; 50 R4 stands for hydrogen, halogen, cyano or nitro and R5 represents C,-, alkyl which may be same or different) which comprises reacting a phenoxy benzoic acid derivative of the general Formula 11 (wherein R', R2, R3 and R4 are as stated in the preamble of this Claim and Y represents halogen, cyano, ethoxycarbonyloxy or tert. butoxycarbonyloxy) with a metal derivative of a malonic acid ester of 55 the general Formula Ill (wherein R5 is as stated in the preamble of this Claim).
11. Process for the preparation of a herbicidal composition according to any of Claims 5-8 which comprises admixing a compound of the general Formula 1 (wherein W' R2, R3, R4 and R5 are as stated in Claim 5) in an amount of 0.01-95% by weight with suitable inert solid or liquid carriers andlor diluents and optionally with further auxiliary agents.
12. Process for controlling weeds which comprises applying onto the objects to be protec ted-preferably onto plants, parts of plants or soil-an effective amount of a compound of the general Formula 1 or a composition comprising the same.
13. A compound of the general formula 1, wherein R' to Rr, are as defined hereinbefore in Table 1.

11 GB2181133A 11
14. A process of making the compounds as claimed in claim 1 substantially as hereinbefore described in any one of Examples 1 to 5.
15. A herbicidal composition substantially as hereinbefore described in any one of Examples 6 to 8
16. A process of making a herbicidal composition substantially as hereinbefore described in 5 any one of Examples 6 to 8.
17. A process for controlling weeds as claimed in claim 12 substantially as hereinbefore described in Example 9.
18. A compound of the general formula 1 wherein the substituents are as defined in claim 1 when made by the process as claimed in claim 9 or 10.
19. A herbicidal composition when made by a process as claimed in claim 11.

Printed for Her Majesty's Stationery Office by Burgess & Son (Abingdon) Ltd, Dd 8991685, 1987.

Published 9: t The Patent Office, 25 Southampton Buildings, London, WC2A 1 AY, from which copies may be obtained.