AU595834B2 - Herbicidal phenoxy benzoyl malonates - Google Patents

Description

Form COMMONWEALTH OF AUSTRALIA PATENTS ACT 1952-69 COMPLETE SPECIFICATION

(ORIGINAL)

Class Int. Class Application Number: Lodged: '6 .3 6 t leg Complete Specification Lodged: Accepted: Published: Priority: nt the Mri fo 0 Holated Art: 04.00 0 00 00 0 0.00 0 0 00 00 0 0 4 0Name of Applicant: 0 00 Address of Applicant: 0 00 0 0 a 0 0 4 00 0 O ctual Inventor: 0004 0 0 00 Address for Service: BUDAPESTI VEGYIUVEK and MTA KOZPONTI KEMIAT KUTATO INTEZET 5, ken Budapest H-1097 and 57-69, Pusztaszeri ut, Budapest II, Hungary TAMAS KOMIVES, FERENC DUTKA, ISTVAN BARTA, ISTVAN JABLONKAI, AGNES HTLESCH, FERENG BIHART, GYUAL ETFERT PETER BOHUS MIHALY NAGY, MIHALY BARABAS and TSTVAN KURONYA EDWD. WATERS SONS, 50 QUEEN STREET, MELBOURNE, AUSTRALIA, 3000.

o. Xomplete Specification for the invention entitled: 0 HERBICIDAL PHENOXY BENZOYL MALONATES The following statement is a full description of this invention, including the best method of performing it known to US 1 -la- HERBICIDAL PHENOXY BENZOYL MALONATES This invention relates to herbicidal phenoxy benzoyl malonates,.a process for the preparation thereof, herbicidal compositions comprising the same and a method for combating weeds by using the said cqmpositions.

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

c t According to an aspect of the present invention t. there are provided new phenoxy benzoyl malonates of the general Formula I 0 S II O 0C-OR

SR

2 C CH

R

3 0 W I c- H "COR 5

(I)

(wherein a a R stands for halogen, cyano, nitro, methylthio, trifluoromethyl, or C 1 4 alkyl; R and R 3 may be the same or different and represent SA 3849-159 KY 2 hydrogen, halogen or trifluoromethyl;

R

4 stands for hydrogen, halogen, cyano or nitro and

R

5 represents Cl-4 alkyl which may be same or different).

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

The new compounds of the general Formula I exhibit a significantly stronger herbicidal effect particularly pre-emergent herbicidal effect than the chemically related known derivatives. The compounds o of the present invention are particularly preferable 4tte when used in pre-emergent application for the o .selective control of grassy and broad-leaved weeds in 04 It 15 various cultures, particularly in maize.

o It In a preferred sub-group of the compounds of the general Formula I R 1 is chlorine or trifluoromethyl, 2 3 R represents chlorine, R stands for hydrogen or chlorine, R is nitro, halogen or cyano and R stands "o 20 for ethyl.

Preferred compounds of the general Formula 'I.

are those in which i stands for trifluoromethyl, *666 2 3 4 .O R represents chlorine, R is hydrogen, R stands for nitro and R is ethyl.

Another preferred group are those compounds of the general Formula I in which R is trifluoromethyl,.

R

2 and R stand for chlorine, R represents nitro and

R

5 is ethyl.

1 i 3-.

A further preferred group are those compounds of the general Formula I in which R1 and R 2 are 3 A R chlorine, R 3 is hydrogen, R stands for nitro and R is ethyl.

The term "C1-4 alkyl" relates to straight or branched chained alkyl groups having 1-4 carbon atoms methyl, ethyl, n-propyl, isopropyl, n-butyl etc.).

According to a further aspect of the present invention there are provided herbicidal compositions comprising as active ingredient 0.01-95 by weight of a compound of the general Formula I (wherein R t 2 4 5 SR R and R are as stated above) in admixture with o suitable inert solid and/or liquid carriers or 00 a 0 .i diluents and optionally auxiliary agents (e.g.

00 0 04 o 0 o S15 surfactants, antifoam, antifreezing and adhesive 0 00 0 0 o0oo agents etc.).

The compositions of the present invention may be 0000 solid or liquid and may be finished in usual forms 0 00 powder mixture, dusting powder, granule, paste, 00 0 2 oo0 20 emulsion, suspension, solution, spray, concentrate etc.).

The compositions comprise diluents and carriers and

S

0 0 0 auxiliary agents generally used in agriculture and 0*oo 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 tractions gas oil or Kerosine), oils of 1 1 1 I 4 animal or vegetable origin; aromatic, aliphatic or alicyclic hydrocarbons benzene, toluene, xylene, cyclohexane, tetrahydro naphthalene etc.) and derivatives thereof chloro benzene, alkyl naphthalenes, cyclohexanol, butanol etc.) or strongly polar solvents dimethyl formamide, dimethyl sulfoxide, N-methyl-pyrrolidone, water etc.) may be used.

The surfactants (emulsifying, dispersing, wetting, antifoam or antiaggregating agents) may be of ionic or non-ionic character. As ionic surfactants c the following compounds may be used: salts of saturated or unsaturated carboxylic acids; sulfonates AO, of aliphatic, aromatic or aliphatic-aromatic hydro- 15 carbons, sulfonates of alkyl, aryl and aralkyl O 0 alcohols; sulfonates of alkyl, aryl and aralkyl alcohols; sulfonates of alkyl, aryl and aralkyl 0o.* carboxylic acids and esters and ethers thereof; 0 44 0 sulfonates of condensation plauds of phenols, cresols 20 or naphthalene; sulfatated oils of animal or vegetable 00 4 origin; alkyl,. aryl or aralkyl phosphate esters; .a 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 and/or propylene oxide and derivatives thereof; alkyl cellulose.

As antifoam agents e.g. ethylent oxide/propylene oxide, condensation products having a low 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, s propylene glycol or glycerol may be used.

The herbicidal compositions of the present a, 15 invention may be prepared by known methods of pesticidal a t industry by admixing at least one compound of the Q tt general Formula I with suitable inert solid and/or Sn liquid carriers or diluents an optionally with foa auxiliary agents.

20 According to a still further aspect of the 01 0 at present invention there is provided a method for controlling weeds which comprises applying onto the l ia objects to be protected preferably onto plants, S° parts of plants or soil an effective amount of a compound of the general Formula I or a composition comprising the same.

According to a still further aspect of the present invention there is provided a process for 6 the preparation of compounds of the general Formula I (wherein R R 2 R 3 R and R 5 are as stated above) which comprises a) reacting a phenoxy benzoic acid derivative of the general Formula II 0 2

I

R

1 Q -0 4

(II)

3 1 2 (wherein R R R 3 and R are as stated in t the preamble and Y represents halogen, cyano or Cl-6 alkyl-carbonyloxy) with a metal t tderivative of a malonate of the general Formula III a a

II

C-OR

CH

2

(III

C-OR

II

0 4 0 0 0 (wherein R 5 is as stated in the preamible) or in the presence of a metal compound preferably magnesium chloride with a malonate of the general Formula III; or b) reacting a phenol of the general Formula IV 7 R1 0-OH -3 CIv) (wherein R 1

R

2 and R 3 are as stated in the preamble) or an alkali metal salt thereof with a benzoic acid derivative of the general Formula V 0 0 ii

SC-OR

C-CH C-OH Z- -R4 II 0 (V ii 0 0 (wherein R and R 5 are as stated in the preamble and Z represents halogen).

According to process a) it is preferred to use a sodium, potassium or magnesium derivative the malonate of the general Formula III. If the malonic acid derivative of the general Formula III 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 benzene, toluene or xylene), an ether diethyl ether, i S- 8 1,2-dimethoxy ethane, tetrahydrofuran or dioxan) an amide dimethyl formamide, hexamethyl phosphoric acid triamide) a ketone acetone or diethyl ketone) or a nitrile acetonitrile) etc. may be used.

The malonic acid derivatives of the general Formula III are reacted in the form of a metal salt thereof with the compound of the general Formula II.

The metal salts of the malonates may be prepared previously e.g. by reacting a malonate of the general Formula III 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 II and III is carried out in the presence of a metal compound preferably magnesium o« chloride. In this case the metal salt of the malonate of the general Formula III is in situ formed in the reaction mixture.

The reaction may be accomplished at a temperature between -10 C and +180 preferably o, at 30-100 0 C. The desired compound is separated by knwon methods after the removal of the by-products formed.

o 0 The malonates of the general Formula III and 00 00 0o 0 metal salts thereof and the starting materials of the general Formula II are partly known compounds.

Such compounds are disclosed in US patent specifications Nos. 3,979,437 and 3,652,645 and in the publications -9 0 0 00 A 0 4 0 O 1 0 0 0 A 0 0 1 oO 4 0 04 OO 4 o o' 0004 o0 4 00 a

QOO

00 0 0 0 Org. Synth. Coll. Vol. 285 and J.Or. Chem. 50, 2622 (1985). The new compounds of the general Formula II 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 IV 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 tort. butylate or any suitable organic base triethyl amine).

Further details of the present invention are 15 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-trifluoro- 20 methyl-phenoxy)-2-nitrobenzoyl-malonate a) To a solution of 38.0 g of 5-(2-chloro-4- -trifluoromethyl-phenoxy)-2-nitro-benzoyl chloride and ml of benzene an ethoxy magnesium malonate solution prepared from 17,6 g of diethyl malonate in 50 ml 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 ml of 10 sulfuric acid are added under stirring. The phases are separated and the aqueous layer is extracted twice with 50 ml 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 0C.

b) A mixture of 19.7 g of 2-chloro-4-trifluoromethyl-phenol, 32,7 g of diethyl-2-nitro-4- -fluoro-benzoyl-malonate and 100 ml of anhydrous dimethyl sulfoxide is stirred at 50 After a a oa reaction time of 24 hours the reaction mixture is ao 15 diluted with 100 ml of water and extracted three times 0 0 0 on o with 50 ml of benzene each. The benzene phase is dried S, over magnesium sulfate and the solvent is distilled 0 0 off. The residual yellow oil is recrystallized from o a mixture of benzene and hexane. Thus 40.3 g of the oo 20 desired compound are obtained, mp.: 72-76 OC.

O a c) A mixture of 21.9 g of sodium-2-chloro-4- -trifluoromethyl-phenolate, 32.7 g of diethyl-2-nitroco o co°°°o -4-fluoro-benzoyl-malonate and 100 ml of anhydrous oo00 00 0 25 dimethyl sulfoxide is stirred at 50 OC for 24 hours.

The reaction mixture is diluted with 100 ml of water and extracted three times with 50 ml of benzene each.

The benzene phase is dried over magnesium sulfate and *i t 11 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-nitro-benzoyl-malonate To a solution of 45.8 g of 5-(2,6-dichloro-4- -trifluoromethyl-phenoxy)-2-nitro-benzoyl bromide in ml of ether a diethyl potassium malonate solution prepared from 17.6 g of diethyl malonate in 50 ml of ether is added dropwise under stirring at room temperature within 20 minutes. The addition having been completed the reaction mixture is refluxed for an hour, cooled and 50 ml of 20 sulfuric acid are added under stirring. The phases are separated, the aqueous layer is extracted twice with 50 ml of ether each. The organic solutions are united, washed successively with water and a sodium hydrogen carbonate 4' solution and the solvent is removed. The residual yellow oil slowly solidifies. Thus 49,9 g of the desired compound are obtained, mp.: 84-88 0

C.

0 0 Example 3 Preparation of diethyl-5-(2-chloro-4-trifluoromethyl-phenoxy) -2-chloro-benzoyl-mialonate To a mixture of 35.0 g of 5-(2-chloro-4-tri- 12 fluoromethyl-phenoxy)-2-chloro-benzoic, and 10.1 g of triethyl amine formed in 100 ml of toluene and cooled to 0 0C with salted ice 12.1 g of pivaloyl chloride are added at a rate that the temperature should not exceed 0 During the addition and the subsequent stirring period (15-20 minutes) triethyl amine hydrochloride precipitates. 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 -5 0C and 0 The reaction mixture is allowed to stand overnight whereupon 200 ml of a 5 sulfuric acid solution are added. The aqueous 15 phase is extracted twice with 50 ml 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 0C.

Example 4 o Preparation of diethyl-5-(2,4,6-trichloroo"a -phenoxy)-2-nitro-benzoyl-malonate 0 0 Into a 500 ml flask equipped with a stirred and a dropping funnel 9.52 g of anhydrous magnesium chloride and 100 ml of anhydrous acetonitrile are introduced. To the heterogenous mixture 16.2 g of

S

1 13 diethyl malonate are added. The flask is placed into an ice bath and 28 ml of triethyl amine are added. To the solution at 0 °C 38.1 g of 5- (2,4,6-trichlorophenoxy)-2-nitro-benzoyl chloride are added dropwise under stirring within 15 minutes. The reaction mixture is stirred at 0 OC for an hour and at room temperature for 12 hours, cooled to 0 0 C, whereupon 60 ml of a 5 lI hydrochloric acid solution are added. The solution formed is extracted three times with 100 ml of ether lo 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 g of the desired f e compound are obtained, mp.: 71-73 °C.

it S 0 Example 4 t The following 19 compounds of the general Formula I enumerated in Table I are prepared in an analoguous manner to the preceding Examples. In the said Table I the definition of symbols R 1

-R

5 the melting points and the characteristic data of the NNR spectra are disclosed.

I

00 00 0 0 0 0 0 I *'i 000 0 0 0 o0 6 0 6 0 6 Table 1 Copud 1 2 3 4 0 .p.1 No. R R R R )H N 1MR (ppm) 1. CF 3 Cl H NO 2 C 2 H5 72-76 1.10 (in, CH 3) 4.1 (in, CH2'' 4.93 CH); 7.6 (in, ar-H) 2. CF 3 Cl Cl NO 2 C 2 H 5 84-88 1.0 (in, CH 3 4.3 (in, CH 2 5.0 CH); 3.0 (in, ar-H) 3. CF3 C l C2H 5 59-65 1.1 (in, CHR 3 4.0 (in, CHR 2 ;4.7 CH); 7.6 ar-H) 4. CF 3 Cl HCl 102C 2

H

5 7-3 10( C iC m r 4. Cl Cl Cl NO C H 627-73' 1.05 (in, CH); 4.0 Cin, CH) 4.9 CH); 7.9 (in, ar-H) 2 2 52 CFl Cl H CN C 2H 5 62-65 1.15 (in, CH 3; 4.1 Cm, IC 2 4.90 CH); 7.7 ar-H) 6. CF 3 Cl H CN C 2 H 5 87-9 1.1 (in, CH 3 4.0 (in, CH 2 4.85 CH), 7.7 ar-H) 8. CF 3 H F NO 2C 2H 5 47-49 1.0 (in, CH 3 4.1 (in, CH 2 4.9 CH); 7.8 ar-H) 9. CH 3 H Cl Br C H oil 0.95 (in, 4.0 (in, CH 2 4.8 Cs, CH); (mn, ar-H) CF H Cl NO CH oil 3.67 4.8 CH); 7.8 (in, ar-H) 3 2 3 11. NO 2 Cl H NO0 2 C2 H 5 oil 1.05 (in, CH 3) 4 .1 (in, CR 2 4.8'7 CH); 7.6 (in, ar-H) 12. CN Cl H Cl C 2

H

5 oil 1.10 (im, CHR 3 4.0 (im, CH 2 4 .7 CR) 7.6 ar-H) 13. CH 3 S C1 H Cl CH 3 oil 3.7 (in, CH 3 j CH 3 4.8 Cs, CH); 7.00 ar-H) 14. Cl CF 3 H NO 2 C 2

H

5 67-71 1.10 (in, 4.0 CR 2 4.80 CH); 7.65 (in, ar-H) CF 3 H C1 NO 2 CH 3 oil 3.71 (in, OCR 3 1.02 (in, CCH 3 3.95 (in, CR 2 4.81 CIO); C 3H 77.6 (in, Ar-H) 4 KT77 ?i:i i i;lrli; 15 Preparation of herbicidal compositions Example 6 Granules having an active ingredient content of 0.01 2.3 g of technical grade compound No. 1 (purity: 89 are dissolved in 97.7 8 of methylene 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.

ir 20 g of the active ingredient premix (2 mm/m solution) 44ad are sprayed onto th granulated carrier through Tees 15 -Jet 10080 nozzles at a rate of 5 g/minutes, whereby the granules are stirred in the Loedige type stirrer S, with a velocity of 50 r.p.m. The sorption type granules are packed.

120 Example 7 p Sprayable powder having an active ingredient of 95 0, 240 g of compound No. 2 (purity 97 o;) g4o previously powdered in a mill equipped with a rotating blade are admixed with 2.5 g of Cab-0-Sil (amorphous silica; carrier) and 7.5 g of type 1494 dispersing agent (sodium salt of the condensation product of sulfonated cresole and formaldehyde) in a 1'1 4 B W -16 mortar. The powdered mixture is ground in a turbine mill (Alpine LMRS-80) under an injected airpressure of 5 bar and a grinding air pressure of 4.5 bar at a feeding rate of 250 g/h. Although the sprayable powder thus obtained contains no separate wetting agent it is readily wettable, and has a mamimal particle size of ,um. In a spray having a concentration of 10 g/1 the floatability at 30 °C after 30 minutes is as follows: 84 in CIPAC standard D water; and 91 in CIPAC standard A water.

o a i 0 0 t 0 a t Example 8 S'Emulsifiable concentrate having an active ingredient content of 24 oa g of Tween 85 (ethoxylated sorbitane trioleate) and 30 g of Sapogenat T-180 (ethoxylated tributyl phenol) emulsifiers and 250 g of technical grade compound No. 7 (purity: 96 are dissolved ,4 in 400 g of cyclohexanone at 40-45 °C under stirring.

When all the components are dissolved the solution of the active ingredient (temperature 40-45 OC) is S' poured into a mixture of 200 g of ionexchanged water and 70 g of ethylene glycol under vigorous stirring 0 whereupon the mixture is cooled to 15-20 C. Before the termination of the stirring period 10 g of Silicon S RE antifoam agent (a 30 emulsion of dimethyl silicon oil) are added to the emulsion and five minutes later 1 r 17 the stirring is stopped.

Example 9 Biological application of the composition Grass seeds and seeds of cultivated plants are sun into sand of the river Danube in plastic boxes (size loxloxlo 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 0 00 0 0 00.0 required for normal plant growth and are kept in a glass 0 0 0 o0000oo 0oo house. The results of the treatment are evaluated after 0 00 oo o a test period of four weeks and assessed with the aid 0 0 So0 15 of a scale from 0 to 10, wherein 0 no symptoms and oo000oo completely destroyed infected plants (100 o 00 As reference compounds two commercially 000 o°o available herbicides are used, namely acifluorfen 0 0 /-chemical name: sodium-5-(2-chloro-4-trifluoromethylo09 S 0 a -phenoxy)-2-nitro-benzoate_7 and oxifluorfen /-chemical name: 2-chloro-l-3-ethoxy-4-nitro-phenoxy)-4-trifluoro- 00o0oo S oaoo methyl benzene_7.

0 0 0 0 S0 0 o 0 The results are summarized in Table II. 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 superior to that of the reference compounds, particularly in pre-emergent application.

18 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 phytotoxical 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.

"T 000 0 0 0 0 0 0 0K O

D

a o o o o o oo a a o 00 0 0 0 00 00 000 0 00 00 so ooo o os o =a O 0 B 0 0 0 o a o I o o "Table Herbicidal activity of the compounds of the general Formula I against various weeds in several cultivated plant cultures in pre-emergent and post-emergent 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 post 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 6 6 8 9 6 6 8 9 4 5 5 8 8 8 10 10 8 8 10 10 6 6 7 8 4 6 5 8 4 6 6 8 4 4 5 6 8 6 5 6 5 0 0 10 8 9 10 10 0 2 8 6 5 6 5 0 0 10 8 9 10 10 0 2 5 4 4 4 4 0 0 6 6 6 8 6 0 2 8 6 5 6. 5 0 0 10 10 10 10 10 1 2 9 7 5 6 5 0 0 10 10 10 10 10 1 2 6 6 4 4 5 0 0 7 8 6 8 6 0 2 4 6 4 5 5 0 0 5 8 6 8 6 0 2 4 6 4 5 5 0 0 6 8 6 8 6 0 2 4 7 4 5 5 0 0 5 8 6 8 6 1 2 0 0 0 4 1 6 1 8 0 0 0 4 1 6 0 8 0 0 0 4 1 3 0 6 0 2 0 4 1 6 1 8 0 2 0 4 1 6 1 8 0 2 0 3 1 6 0 6 0 2 0 3 1 6 0 6 0 2 0 3 1 6 0 6 0 2 0 3 1 6 0 6 0 6 2 0 6 2 L 1_1 -a ab y (Continuation of Ta e II) (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 0.3 8 10 6 10 8 8 8 8 0 0 0 2 0 4 0 6 10 10 9 10 10 10 10 10 1 2 1 7 2 8 2 11. 0.3 6 4 6 6 7 6 6 5 0 0 0 0 0 4 0 8 5 7 8 8 7 10 8 0 2 1 6 1 6 2 12. 0.3 6 4 5 6 8 6 7 5 0 0 0 0 0 3 1 6 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 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 8 6 8 7 9 8 10 10 0 2 1 6 1 8 0 8 0.3 6 7 6 7 6 6 5 6 0 0 0 0 0 4 0 6 8 9 10 9 9 9 10 10 0 2 1 6 1 8 2 acifluorfen 0.3 6 7 5 7 8 6 8 7 3 0 4 2 6 4 6 6 reference 1.0 8 10 8 10 8 9 10 10 6 2 8 7 8 8 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

Claims (13)

1. Phenoxy-benzoyl-malonates of the general Formula I 0 0 II 0 C-OR' R I R 4 C OR 5 (I 3 0 (wherein S. R 1 stands for halogen, cyano, nitro, methylthio, trifluromethyl or C,-4 alkyl; o 2 3 R and R may be the same or different and represent 0"e hydrogen, halogen or trifluoromethyl; 0 a R 4 stands for hydrogen, halogen, cyano or nitro and R 0° represents alkyl which may be same or different). o 0

2. Compound according to Claim 1 wherein R 1 stands for trifluoromethyl, R 2 represents chlorine, R 3 is hydrogen, R 4 stands for nitro and R 5 is ethyl. 0000 0 00 0 00°°

3. Compound according to Claim 1 wherein R 1 is trifluoromethyl, R 2 and R 3 stand for chlorine, R 4 represents 00 5 s °e.o nitro and R is ethyl.

4. Compound according to Claim 1 wherein R 1 and R 2 are 0o oo chlorine, R 3 is hydrogen, R 4 stands for nitro and R 5 is f ethyl. Herbicidal composition comprising as active ingredient in an amount of 0.01-95% by weight a phenoxybenzoyl malonate of the general Formula I 0 II .2 CH R 4 c-oR R I S0 A: -22- (wherein R stands for halogen, cyano, nitro, methylthio, trifluromethyl or C1_ 4 alkyl; R 2 and R 3 may be the same or different and represent hydrogen, halogen or trifluromethyl; R 4 stands for hydrogen, halogen, cyano or nitro and R represents C_ 4 alkyl which may be same or different) in admixture with suitable solid and/or liquid carriers preferably silicic acid, silicium dioxide and/or cyclohexanone and optionally auxiliary agents preferably surfactants, such as ethoxylated tributyl phenol or an alkyl sulfonate.

S.

6. Herbicidal composition according to Claim comprising as active ingredient a compound of the general Formula I wherein R 1 stands for trifluoromethyl, R 2 o represents chlorine, R 3 is hydrogen R 4 stands for nitro and S' R 5 is ethyl.

7. Herbicidal composition according to Claim comprising as active ingredient a compound of the general \Formula I wherein R 1 is trifluoromethyl, R 2 and R 3 stand for chlorine, R 4 represents nitro and R 5 is ethyl. 0 0 :o

8. Herbicidal composition according to Claim comprising as active ingredient a compound of the general Formula I wherein R 1 and R 2 are chlorine, R 3 is hydrogen, R 4 So*, stands for nitro and R 5 is ethyl.

9. Process for the preparation of phenoxybenzoyl malonates of the general Formula I 6 11 0. C-OR 2 c C H R t 1 'R 23 (wherein R stands for halogen, cyano, nitro, methylthio, trifluoromethyl or C 4 alkyl; R 2 and R 3 may be the same or different and represent hydrogen, halogen or trifluoromethyl; R 4 stands for hydrogen, halogen,'cyano or nitro and R s represents C 1 4 alkyl which may be same or different) which comprises a) reacting at a temperature between -100 and So", +1800 a phenoxy benzoic acid derivative of the a 4o general Formula II o 00 0 00 S* 2 0 0 2 11 SC-Y SR R 4 (II) R 00,@ S00 I 3 4 0 ,(wherein R R R and R are as stated in or C 1 6 alkyl-carbonxyloxy) in the presence of an inert solvent wita an alkali metal alkaline earth metal derivative of a malonate of the o general Formula III 0 04 C-OR CH (III C-OR II 0 S< (wherein R is as stated in the preamble) or in Sthe presence of an alkali metal or alkaline earth metal 7 compound preferably magnesium chloride with a malonate of the general Formula III; or tif R 24 b) reacting a phenol of the general Formula IV R2 Rl-0 (IV) 3 (wherein R R 2 and R 3 are as stated in the preamble) or an alkali metal salt thereof with a benzoic acid. derivative of the general oO Formula V a 4 0 0 0 o 0 S00 1 oi o4 0 II C 0 C-OR 0 C-CH C- 00 0R C-OR Z- w-R 4 5 V 0*0 A(wherein R 4 and R 5 are as stated in the o 0 preamble and Z represents halogen). 00-46

10. A process according to claim 9 for the preparation 0 0 a of phenoxy-benzoyl malonates of the general formula I as Sclaimed in any one of claims 1 to 4 wherein the alkaline earth metal derivative of a malonate of the general 0 0 formula III is magnesium.

S11. Process for the preparation of phenoxy-benzoyl malonates of the general Formula I (wherein R stands for halogen, cyano, nitro, methylthio, trifluromethyl or C_-4 alkyl; R 2 and R 3 may be the same or different and represent hydrogen, halogen or trifluoromethyl; R 4 stands for hydrogen, halogen, cyano or nitro and R 5 represents Ci_4 alkyl which may be same or different) which comprises reacting at a temperature between -10 0 C and S/ +180° a phenoxy benzoic acid derivative of the general 25 Formula II (wherein R R 2 R 3 and R 4 are as stated in the preamble of this Claim and Y represents halogen, cyano, ethoxycarbonyloxy or tert. butoxycarbonyloxy) in the presence of an inert solvent with an alkali metal or alkaline earth metal derivative of a malonic acid ester of the general Formula III (wherein R 5 is as stated in the preamble of this Claim).

12. Process for the preparation of a herbicidal composition according to any of Claims 5-8 which comprises admixing a compound of the general Formula I (wherein R 1 2 3 4 5 R R R and R are as stated in Claim 5) in an amount of 0.01-95% by weight with suitable inert solid or liquid o* carriers and/or diluents and optionally with f.-ther 0n auxiliary agents. On 00

13. Process for 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 I or a composition comprising the same. 0 0 DATED this 21st day of June, 1989 00 0 0 BUDAPESTI VEGYIMUVEK and MTA KOZPONTI KEMIAI KUTATO INTEZET S a °WATERMARK PATENT TRADEMARK ATTORNEYS Queen Street MELBOURNE. VIC. 3000 AUSTRALIA LCG:KJS:SC(1.35) "2