FR2587998A1 - PHENOXY-BENZOYL-MALONATES, PREPARATION THEREOF AND HERBICIDE COMPOSITIONS CONTAINING SAME - Google Patents

Abstract

GENERAL FORMULA PHENOXY-BENZOYL-MALONATES: (CF DRAWING IN BOPI) (OR R REPRESENTS HALOGEN, CYANO, NITRO, METHYLTHIO, TRIFLUOROMETHYL OR CAC ALCOHOL; R AND R MAY BE SIMILAR OR DIFFERENT, HYANO, NITRO, METHYLTHIO, TRIFLUOROMETHYL OR ALCOHYL; R AND R MAY BE SIMILAR OR DIFFEREFLENTAL, HY, ROMETRO, ROMETRO, OR DIFFENENTAL, ROMETRO, ROMETRO REPRESENTS HYDROGEN, HALOGEN, CYANO OR NITRO AND R REPRESENTS ALCOHYL IN CAC AND MAY BE SIMILAR OR DIFFERENT).

Description

i

  The present invention relates to phenoxy-benzoyl-malo

  herbicides, a process for their preparation, herbicidal compositions comprising these compounds and a method for combating

  weeds by use of said compositions.

  It is known that certain phenoxy-benzo acid derivatives

  have a herbicidal effect. These compounds are described in the

  vets No. 3,979,437 and 3,652,645.

  According to one aspect of the invention there is provided new phenoxy benzoyl malonates of general formula I

O C-OR5

I /

R2 - CH

Ri_4 / 04 C-OR5 R. o - -R "iI

30

  R 3 (where R represents halogen, cyano, nitro, methylthio, or (C 1 -C 4) alkyl; R 2 and R 2 may be the same or different and is hydrogen, halogen or trifluoromethyl; R 4 is hydrogen, nalogen, cyano or nitro (C 1 -C 4) alkyl which may be similar or (I) trifluoromethyl

represent hy-

  and R represents different). The new compounds of the general formula I differ from the known derivatives in the structure of the fraction attached to the

carbonyl group.

  The new compounds of the general formula I exhibit a significantly higher herbicidal effect - in particular a pre-emergence herbicidal effect - than the chemically known derivatives.

  related. The compounds of the invention are particularly preferably

  feable when used in a pre-emergent application.

  for selective control of grass and broadleaf weeds in various crops, particularly in maize.

  In a preferred subgroup of compounds of general formula

  R 1 is chlorine or trifluoromethyl, R 2 is chlorine, R 3 is hydrogen or chlorine, R is nitro,

  halogen or cyano and R represents an ethyl.

  The preferred compounds of general formula I are those where R1 represents trifluoromethyl, R2 represents chlorine, R3 is

  hydrogen, R4 is nitro and R5 is ethyl.

  Another preferred group is that of compounds of general formula I wherein R 1 is trifluoromethyl, R 2 and R 3 represent a

  chlorine, R4 is nitro and R5 is ethyl.

  Another preferred group is that of the compounds of general formula I where R 1 and R 2 represent a chlorine, R 3 is a hydrogen,

  R4 represents a nitro and R5 is an ethyl.

  The term "C1-C4 alkyl" refers to groups

  straight or branched chain coyl having 1 to 4 carbon atoms

  (methyl, ethyl, n-propyl, isopropyl, n-butyl, etc.).

  According to another aspect of the invention there is provided herbicidal compositions comprising 0.01 as an active ingredient

1 2 4

  to 95% by weight of a compound of the general formula I (o R, R, R and

  R are as defined above) mixed with diluted

  solid and / or inert liquids and optionally auxiliary agents (for example surfactants, antifoams,

  anti freezing and adhesives, etc.).

  The compositions of the invention can be solid or liquid and can be finished in the usual forms (for example powder mixture, powder for dusting, granule,

  paste, emulsion, suspension, solution, sprayed liquid, concentrated

  very, etc.). The compositions comprise diluents and

  ports, and auxiliary agents generally used in agriculture.

  culture and in plant protection.

  Solid supports may be inorganic materials

  or synthetic, for example kaolin, siliceous earth, talc, attapulgite, diatomaceous earth, alumina, acid

  silicic acid and various silicates. As liquid diluent one can u-

  for example, use mineral oil fractions (eg

  diesel or kerosene), oils of animal or vegetable origin

  tale; aromatic, aliphatic or alicyclic hydrocarbons

  (eg benzene, toluene, xylene, cyclohexane, tetrahydro-

  naphthalene, etc.) and their derivatives (for example chlorobenzene,

  coyle naphthalines, cyclohexanol, butanol, etc.) or solvents

  strongly polar (eg dimethylformamide, dimethyl

  sulfoxide, N-methyl-pyrrolidone, water, etc.).

  Surfactants (emulsifying agents, dispersing agents,

  wetting, anti-foaming or anti-caking agents) may be ionic or nonionic in nature. As ionic surfactants, the following compounds may be used: saturated or unsaturated carboxylic acid salts; Hyd sulfonates = aliphatic, aromatic or aliphatic-aromatic carbides, sulfonates

  alkyl aryl and aralkyl alcohols; alkyl sulfonates, aryl

  and aralkyl-alcohols; sulfonates of alkyl, aryl and aralkyl carboxylic acids and their esters and ethers; sulphonates of condensation products of phenols, cresols or naphthalene; sulphated oils of animal or vegetable origin; Alkyl esters -,

  aryl or aralkyl phosphate; sulphonates and phosphates of polygly-

  ethylene oxide ethers formed with the fatty alcohols or alcohols

coyl - phenols.

  As nonionic surfactants it is possible to use

  for example the following compounds: condensation products of ethyl-

  ethylene oxide formed with fatty alcohols; alkyl aryl polyglycol

  ethers; polymers of ethylene oxide and / or propylene oxide and

their derivatives; alkyl cellulose.

  Examples of anti-foaming agents that may be used are ethylene oxide / propylene oxide condensing products having a low molecular weight; aliphatic alcohols; the

  special silicone oils or fatty acid amides.

  Adhesive or thickening agents that may be used include, for example, alkaline earth metal soaps, sulphosuccinic acid ester salts; or natural or synthetic macromolecular materials that are soluble or can swell in water. As anti-freezing agent it is possible to use for example

  ethylene glycol; propylene glycol or glycerol.

  The herbicidal compositions of the invention can be prepared.

  by methods known to the pesticide industry in

  at least one compound of the general formula I with

  solid ports and diluents and / or suitable inert liquids and

  possibly with auxiliary agents.

  According to yet another aspect of the invention there is provided a method for controlling weeds in which the objects to be protected are applied - preferably on

  plants, parts of plants or the soil - an amount of

  ficace of a compound of general formula I or a composition

  comprising a compound of general formula.

  According to yet another aspect of the invention there is provided a process for the preparation of compounds of the general formula I (o 1 2 3 4 5 -ess R 1, R 2, R 3, R 4 and R are as defined above) in which a) reacting a phenoxybenzoic acid derivative of general formula II o I

2 C-Y

  Wherein R, R2, R and R are as defined in the preamble and Y is halogen, cyano or C1-C6 alkylcarbonyloxy) with a derivative; metal of a malonate of general formula III on C-OR5

CH2 III

  C-OR5 is as defined in the preamble) 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 general formula IV R2

R1-H IV)

2 3

  R, R and R are as defined in the preamble

  (e) or an alkali metal salt thereof with a benzoic acid derivative of the general formula ## STR2 ##

/ C-CH> 05

C-OR z b 5 14 1 (V)

4 5

  (o R and R are as defined in the preamble

and Z represents a halogen).

  According to method a), the malonate of the general formula III is preferably used as the sodium, magnesium or potassium derivative. If the malonic acid derivative of general formula III is used as such, it is preferred to carry out the reaction in the presence of a magnesium compound, in particular magnesium chloride.

  as a metal compound. The reaction can be carried out preferably

  in an inert solvent. As a solvent it is interesting to

  use a hydrocarbon (eg benzene, toluene or xylene),

  an ether (for example diethyl ether, 1,2-dimethoxyethane, tetrahydro-

  furan or dioxane) an amide (for example dimethylformamide,

  hexamethylphosphoric acid amide), a ketone (e.g.

  acetone or diethyl ketone) or a nitrile (eg acetonitrile), etc.

  The malonic acid derivatives of general formula are reacted

  III in the form of a metal salt thereof with the compound of general formula II. We can prepare beforehand

  metal salts of malonates, for example by reacting a

  lonate of general formula III with an alkali metal compound or

  alkaline earth or an organic metal compound. According to an aw

  The reaction is carried out with compounds of the general formula

  II and III in the presence of a metal compound - preferably

  magnesium chloride. In this case the metal salt of

  of general formula III is formed in situ in the reaction mixture.

  tional. The reaction can be carried out at a temperature of between 10 C and +180 C, preferably at 30-100 ° C. We separate the

  desired by known methods after removal of the

shapes.

  The malonates of general wheat cheese III, and their salts

  and the starting materials of the general formula II are partially known compounds. These compounds are described in

  U.S. Patent Nos. 3,979,437 and 3,652,645 and in the

  cations Org. Synth. Coll. Flight. 285 and J. Or. Chem. 50, 2622 (1985).

  The novel compounds of general formula can be prepared

  II in a similar way to the process described in the so-called publica-

tions.

  According to process b) the compounds of formula

  the general IV and V preferably in the presence of a solvent or dilu-

  inert ant. As reaction medium it is possible to use the solvents

  described above in connection with process a). We prefer working

  in the presence of an acid-binding agent, for example a hydroxide

  alkali carbonate, an alkaline ethoxide or a tert.buty-

  alkaline or any suitable organic base (e.g.

eg triethylamine).

  Further details of the invention can be found in the examples

  following, without limiting the scope of protection to

examples.

EXAMPLE 1

  Preparation of diethyl-5- (2-chloro-4-trifluoromethyl-phenoxy) -2-

nitrobenzoyl-malonate.

  a) To a solution of 38.0 g of 5- (2-chloro-4-

  trifluoromethyl-phenoxy) -2-nitro-benzoyl and 50 ml of benzene on

  add a solution of ethoxy magnesium malonate prepared at

  17.6 g of diethyl malonate in 50 ml of benzene at

  room temperature while stirring for 20 minutes. After the end of the addition, the reaction mixture is refluxed for one hour and then cooled. To the viscous solution was added 50 ml of 20% sulfuric acid with stirring. The phases are separated and the aqueous layer is extracted twice with 50 ml of benzene each time. The combined extracts are washed with water and a solution of

  sodium hydrogen carbonate, after which the solvent is removed by distillation.

  tillation. The residual yellow oil slowly becomes crystalline.

  There is thus obtained 47.8 g of the desired compound, mp 72-76 C.

  b) A mixture of 19.7 g of 2-chloro-4- is stirred at 50 [deg.] C.

  trifluoromethylphenol, 32.7 g of diethyl-2-nitro-4-fluoro-benzoyl-

  malonate and 100 ml of anhydrous dimethylsulfoxide. After one

  reaction time of 24 hours the reaction mixture is diluted with

  ml of water and extracted 3 times with 50 ml each of

  zene. The benzene phase is dried over magnesium sulphate and

  raise the solvent by distillation. The residual yellow oil is recrystallized from a mixture of benzene and hexane. We obtain

  thus 40.3 g of the desired compound, mp 72-76 C.

  c) A mixture of 21.9 c of sodium 2-chloro-4-trifluoromethylphenolate, 32.7 g of diethyl-2-nitro-4-fluorobenzoyl-manolate and 100 ml of anhydrous dimethylsulfoxide is stirred at 50 ° C. for 24 hours. . The reaction mixture is diluted with 100 ml of water and ex. run 3 times with 50 ml of benzene each time. We dry the phase

  benzene over magnesium sulphate and the solvent is removed

  tillation. The residual yellow oil is recrystallized from a mixture of benzene and hexane. 39.8 g of the compound are thus obtained

desired, mp 72-76 C.

EXAMPLE 2

  Preparation of diethyl-5 (2,6-dichloro-4-trifluoromethylphenoxy) -

2-nitro-benzoyl-malonate

  To a solution of 45.8 g of 5- (2,6-dichlorobenzene) bromide

  4-trifluoromethyl-phenoxy) -2-nitro-benzoyl in 50 ml of ether

  dropwise a solution of diethyl potassium malonate

258'7998

  sium prepared from 17.6 g of diethyl malonate in 50 ml

  of ether while stirring at room temperature for 20 minutes.

  utes. After the end of the addition the mixture is refluxed.

  during 1 hour, the mixture is cooled and 50 ml of

  sulfuric acid at 20% while stirring. We separate the phases, we ex-

  twice the aqueous layer with 50 ml of ether each time.

  The organic solutions are combined, washed successively with water and a solution of sodium hydrogen carbonate and the solvent is removed. The residual yellow oil solidifies slowly. We

  thus obtained 49.9 g of the desired compound, mp 84-88 C.

EXAMPLE 3

  Preparation of diethyl-5- (2-chloro-4-trifluoromethylphenoxy) -2-

cnloro-benzoyl-malonate

  To a mixture of 35.0 g of 5- (2-chloro-4-trifluoro-

  methyl-phenoxy) -2-chlorobenzoic acid, and 10.1 g of triethylamine formed in 100 ml of toluene and cooled to 0 ° C. with ice-water, 12.1 g of pivaloyl chloride are added at such a rate that temperature does not exceed 0 C. During the addition

  and the subsequent period of agitation (15-20 minutes) it becomes clear

  pite triethylamine hydrochloride. We replace the funnel to

  valve of pivaloyl chloride by a conical funnel

  holding a solution of ethoxymagnesium malonate prepared from

  17.6 g of diethyl malonate. During the drop-in addition

  of the ether solution the temperature is kept at a value

  between -5 ° C and 0 ° C. The reaction mixture is allowed to stand.

  overnight, after which 200 ml of a 5% sulfuric acid solution are added. The aqueous phase is extracted twice with 50 ml of ether each time. The combined organic extracts are washed

  with dilute sulfuric acid and a solution of

  of sodium, dried over anhydrous sodium sulphate and

  vaporer. 44.3 g of the desired compound are obtained in the form of crystals.

  slightly yellowish rates; mp 59-65 C.

EXAMPLE 4

  Preparation of diethyl-5- (2,4,6-trichlorophenoxy) -2-nitro-benzoyl

malonate

  In a 500 ml flask equipped with a stirrer and a

  9,52 g of anhydrous magnesium chloride and 100 ml of anhydrous acetonitrile are introduced. To the heterogeneous mixture was added 16.2 g of diethyl malonate. The flask is put in an ice bath and 28 ml of triethylamine are added. At 0 C solution

  added dropwise 38.1 g of 5- (2,4,6-trichloro-

  phenoxy) -2-nitro-benzoyl with stirring for 15 minutes. We

  The reaction mixture is stirred at 0 ° C. for 1 hour and at room temperature.

  room temperature for 12 hours, cooled to 0 ° C, after which

  60 ml of a 5M solution of hydrochloric acid are added. We ex-

  3 times the solution formed with each 100 ml of ether,

  the combined extracts are dried over magnesium sulphate and

  ve the solvent and traces of diethyl malonate. Light oil

  residual yellowish color slowly solidifies. We obtain

  0 g of the desired compound, mp 71-73 C.

EXAMPLE 5

  The following 19 compounds of the general formula I listed are prepared

  in Table I in a similar manner to the previous examples. In the-

  said table I the definitions of the symbols R1-R5 are given

  if the melting points and the characteristic data of the

NMR spectra.

  1 22 B3 1 5 'B5 (OC) 1. 2. 3. 4. 51. 6. ?. at. 9., 11. 12. 13. 14. CF3 cK3 Cl CF3 CF3 CF3 cH3 Ci CF3 CF3 CF3 Cil3 CF3 NO2 CN CH3S Ci

15. CF3

  ## STR2 ##

C1 H CN C2H5

FH H C2H5

C1 ClC

H F NO2 C2H5

CH Cl Br2 C2H5

H C C H N02 CH3

C1Fi N2 C2H5

C 1 H C 1 C 2 H 5

Ci H CH CH C2H5

F H H C2H5

HC F 3H NO2 C2H5

  C25 HCl1 Cl C H Cl NO2 CH3 C3H Cl H NO2 C2H Cl C1 Cl C2H5 C1 Cl Cl CH3

CF3 H O2C2H

  HCl NO2 CH3 C3H 72-76 84-88 59-65 71-73 62-65 87-93 oil 47-49 oil oil oil oil oil 67--1 oil 1.10 (min, CH3); 4.1 (min, CH 2); 4.93 (s, CH); 7.6 (min, ar-H1) 1.0 (min, CH3); 4.3 (m, CH 2); 510 (s, CH); 8.0 (m, ar-H) 1.1 (min, CH 3); 4.0 (min, CH 2); 4.1 (s, CH); 7.6 (m, ar-H) 1 y (rm, CH 3); 410 (mni, CH 2); 4.95 (s, CH); 7.9 (nl, ar-H) 1.15 (m, CH); 4.1 (mni, CH 2); 4.90 (s, CH); 7.7 (m, ar-H) 1.1 (min, CH 3); 4.0 (m, CH 2); 4.85 (s, CH); 7.7 (min, ar-H) 1.0 Ia, CH3); 4; 0 (m, CHl 2); 4.8 (s, CH); 7.8 (min, arIH) 1.0m, CH3); 4y1 (m, CH2); 4.9 (s, CH); 7; 8 (m, ar-H) 0.95 (m, CH 3); 4.0 (min, CH 2); 4.8 (s, CH); 7t7 (m, ar-11) 3.67 (s, CH 3); 4.8 (s, CH); 7, 8 (min, ar-H) 1.05 (m, CH 3); 4.1 (m, CH 2); 4.87 (s, CH); 7.6 (m, ar-H) 1, 10 (m, CH 3); 4.0 (m, CH 2); 4.7 (s, CiH); 7.6 (t, ar-1H) 3.7 (min, CH 3, CH 3 S); 4Y8 (s, CH); 7.0 (min, ar-H) 1; 10 (m, CH 2); 4.0 (m, C12); 4.80 (s, CH); 7.65 (n, ar-fi) 371 (im, OCH3); 1.02 (ml CCH3); 3.95 (m, CH 2); 4.81 (s, ClI); 7.6 (m, Ar-1) H compound No.

TABLE I

  NMR (ppnm) N CoN CO Co Preparation of herbicidal compositions

EXAMPLE 6

  Granules with an active ingredient content of 0.01%

  2.3 g of compound No. 1 of industrial grade are dissolved

  (89% purity) in 97.7 g of methylene chloride to give a solution having a concentration of 2% by weight. An acidic beaded siliceous earth support prepared from 4000 g of diatomaceous earth is placed in a Loedige turbine agitator of the type; the average pacticular size of the support is between 0.5

  and 2 mm. 20 g of the premix of active ingredient (so-called

  2% mm / m 2) on the granulated support through 10080 jet nozzle nozzles at a rate of 5 g / min, so that the granules are agitated in the Loedige type agitator at a rate of

  r.p.m. The sorption-type granules are chopped.

EXAMPLE 7

  Sprayable powder with 95% active ingredient content

  240 g of compound n 2 (purity 97%) are mixed beforehand.

  powder in a mill equipped with a rotating blade

  2.5 g of Cab-O-Sil MS (amorphous silica, support) and 7.5 g of 1494 dispersant (sodium salt of the cresol sulfon condensation product and formaldehyde) in a mortar. . The powder mixture is ground in a turbine mill

  (Alpine LMRS-80) under an injected air pressure of 5 bars and

  no crushing air pressure of 4.5 bar at a load speed of 250 g / hour. Although the pulverizable powder thus obtained does not

  no separate wetting agent, it is easily wetted

  lable, and has a maximum particle size of 20 micrometers.

  In a spray product having a concentration of 10 g

  per liter the buoyancy at 30 C after 30 minutes is the following

* boasts: 84% in standard CIPAC water D; and 91% in standard CIPAC water.

EXAMPLE 8

  Emulsifiable concentrate having an active ingredient content of 24% 40 g of Tween 85 (ethoxylated sorbitan trioleate) and 30 g of Sapogenat T-180 (ethoxylated tributylphenol) are dissolved

  as emulsifiers and 250 g of industrial grade compound 7

  trielle (purity 96%) in 400 g of cyclohexanone at 40-45 C while stirring. When all the components are dissolved, the solution of the active ingredient (temperature 40-45 C) is poured into a

  mixture of 200 g of ion-exchanged water and 70 g of ethyl

  binds glycole while stirring vigorously after which

  chills the mixture to 15-20 C. Before the end of the stirring period

  10 g Silicon SRE antifoaming agent (emulsion with% dimethyl silicone oil) are added to the emulsion and 5 minutes more

later we stop shaking.

EXAMPLE 9

  Biological application of the composition Seeds of herbs and cultivated plants are sown in Danube sand in plastic boots

  (size 10 X 10 x 10 cm) and pulverized compositions

  prepared from the emulsifiable concentrates of the compounds

  sand surface (pre-emergent treatment) and 3 weeks after seeding (post-emergence treatment). Plastic boxes are emulsified at the rate required for normal growth of the plants and held in a glasshouse. The results of the treatment are evaluated after a 4 week experimental period and measured on the wing.

  on a scale from 0 to 10 o 0 = no symptom and 10 = plan

  infected patients completely destroyed (100%).

  As reference compounds two herbicides are used

  of trade, namely acifluorfen [chemical name: 5- (2-chloro-

  Sodium 4-trifluoromethyl-phenoxy) -2-nitro-benzoate] and oxiflu-

  orfen [chemical name: 2-chloro-1- (3-ethoxy-4-nitro-phenoxy) -4-

trifluoromethyl benzene].

  The results are summarized in Table II. It appears from the said data that the activity of the present compounds

  - in the form of the average activity against the bad her-

  graminaceous and broadleaf - is superior to that of the reference compounds, especially in the pre-emergence application.

  The tolerance of a certain number of

  grown in the compositions of the invention by the methods of treatment described in this example. Dicotyledonous crops were found to tolerate well

  compositions of the invention and that at the herbicidal dose above

  any of the compounds of the invention do not cause any phy-

  totoxique. It has also been found that while in treatment of

  pre-emergent corn, sunflower and leguminous plants to-

  compounds of the invention, only soy tolerates

  oxifluorfen and acifluorfen used as reference compounds.

ence.

Table II

  Herbicidal activity of the compounds of the general formula I against various weeds in several crops of plants grown in a pre-emergence and post-emergence treatment compound exp. bose klG unaranthus Chenopodium Echinochloa Setaria soybean but N of lngredient / hi remtroflexus album crus-gall [italica ac tlt i pr'e post pm. post p post po post pm post post pre pre post sunflower post post

6 6 6

9 8 9

6 6 6

9 8 9

4 5

8 5 8

9 8 8

10 10

9 8 8

10 10

6 6 6

8 7 8

6 4 6

8 5 8

4 4 6

6 6 8

"4 4

6 5 6

8 6

8

8 6

8

4

6 6

8 6

10

9 7

10

6 6

7 8

4 6

8

4 6

6 8

4 7

8

6 5

9 10 10

6 5

9 10 10

4 4 4

6 8 6

6 5

10 10

6 5

10 10

4 4 5

6 8 6

4 5 5

6 8 6

4 5 5

6 8 6

4 5 5

6 8 6

  0 o 0 2 O O 0 2 0 0 0 2 0 0 1 2 0 0 1 2 0 0 0 2 0 0 0 2 0 0 0 2 0 0 1 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

  1. 2. 3. 4. 5. u, 3 1.0 0.3 1.0 0O3 0.3 1.0 0.3 1.0 0.3 1.0 0.3 o 0.3 1, 0 0.3 1.0 6. 7. 8. L /, 9.

0 6

2 10

0 6

2 10

0 6

O 8

o 6

2 8

0 6

2 8

0 6

0 8

0 6

0 8

0 6

0 U

0 6

O 8

  CO 4 \ 0 \ 0 Co ao (continued from Table II)

co-deposited exp.

  compound exp. Dose kg Amaranthus Chenopodium Echinochloa Setaria soybean pea but sunflower n Ingredient / ha retroflexus album crus-galli italica active pre post pre post pre post pre post post post re po st re post pre post pre post post

8 10 6

10 9

6 4 6

8 5 7

6 4 5

7 5 7

4 4 4

7 6 6

8 10

6 7

8 8

6 8

8 10

4 5

8

8 8 8

10 10

6 6 5

7 10 8

0 0 0 2 0 4

1 2 1 7 2 8

0 0 0 0 0 4

0 2 1 6 1 6

6 7 5 0 0 0 0 0 3

8 6 0 1 1 5 1 6

5 5 0 0 0 0 O 3

6 8 6 I 2 1 3 1 5

0 6

2 10

0 5

2 10

1 6

2 6t;

0 5

1 6

  14. 15. fluorfen aci (reference) oxifluorfen (reference) Or3 1.0 0.3 1.0 Or3 lyO 0.3 1; 0

6 5 7

8 6 8

6 7 6

8 9 10

6 7 5

8 10 8

6 6 6

8 10 8

6 7

7 9

7 6

9 9

7 8

8

6 8 7

8 10 10

6 5 6

9 10 10

6 8 7

9 10 10

6 6 8 6 7

8 10 10 10

0 O O O 0 4

0 2 1 6 1 8

0 0 0 0 0 4

0 2 1 6 1 8

0 6

0 a

0 6

2 10

3 0 4 2 6 4 6 6

6 2 8 7 8 8 10 10

3 0 4 3 6 4 6 6

6 3 9 8 8 9 10 10

  10. 11. 0.3 1.0 0.3 1.0 t1.0 12. 13. 0.3 1.0r a 'o Co Co

Claims (10)

R E V E N D I C A T IO N S   1. Phenoxybenzoyl malonates of the general formula I o   C-_OR5 a2 I f R2 C CH Ri_ O_ 4_R4 C-OR (I) II R3 (o   R1 represents halogen, cyano, nitro, methylthio, trifluoromethyl   thyl or C1 to C4 alkyl; R2 and R may be the same or different and represent hydrogen, halogen or trifluoromethyl;   R4 represents hydrogen, halogen, cyano or nitro and R represents   C1 to C4 alkyl and may be the same or different).   2. Compound according to claim 1, wherein R represents a trifluoro-   rom, R2 is chlorine, R is hydrogen, R is   a nitro and R is an ethyl (priority October 1, 1985).   3. The compound according to claim 1, wherein R is a trifluoromethyl   the, R2 and R3 represent a chlorine, R4 represents a nitro and R is an ethyl.   4. Compound according to claim 1, wherein R and R represent a chlorine, R is a hydrogen, R represents a nitro and R is an ethyl. 5. Herbicidal composition comprising as active ingredient in an amount of 0.01-95%. weight a phenoxy-benzoyl malonate of general formula I o O0 5 _R2 cCO C-OR R2 C -CH RI - O_ _CR-4 (C t ' R3 O   (R1 represents halogen, cyano, nitro, methylthio, trifluoromethyl or C1-C41 alkyl; R2 and R3 may be the same or different and represent hydrogen, halogen, or trifluoromethyl;   R4 represents hydrogen, halogen, cyano or nitro and R represents   C1 to C4 alkyl may be the same or different) mixed with suitable solid and / or liquid carriers - preferably silicic acid, silicon dioxide and / or cyclohexanone - and optionally auxiliary agents - preferably surfactants, such as tributyl phenol ethoxylated or an alkyl sulfonate.   6. Herbicidal composition according to claim 5   taking as active ingredient a compound of the general formula I o R 1 represents a trifluoromethyl, R 2 represents a chlorine,   R3 is hydrogen, R4 is nitro and R is ethyl.   7. The herbicidal composition of claim 5 further comprising   as active ingredient a compound of the general formula I o R is trifluoromethyl, R and R are chlorine, R4   represents a nitro and R5 is an ethyl.   The herbicidal composition of claim 5 further comprises   as active ingredient a compound of the general formula I o R1 2 34   R1 and R are chlorine, R is hydrogen, R4 is   feel. a nitro and R is an ethyl 9. A process for the preparation of pheenoxybenzoyl malonates of the general formula I O O   Z -OR5 R / C CH I # / R 1- R 4 C-OR5 1.O_X. R4 (o   R1 represents a halogen, cyano, nitro, methylthio, triflv: oro-   methyl or C1 to C4 alkyl; R2 and R3 may be the same or different and represent hydrogen, halogen or trifluoromethyl;   R4 represents hydrogen, halogen, cyano or nitro and R repre-   C1 to C4 alkyl may be the same or different) in which a) a phenoxy-benzoic acid derivative is reacted with the general formula II O ' RE C-Y R3 (o R, R2 3 4   (or R R, R R and R are as defined in the pre-   and Y represents halogen, cyano or C 6 -carbonyloxy) with a metal derivative of a malonate of the general formula III o0 I 5 COR CH2 (III)   c-OR5 It o0 o R5 is as defined in the preamble) or   in the presence of a metal compound - preferably   magnesium chloride - with a melon-   te of general formula III; or b) reacting a phenol of general formula IV R2 R OH (IV) 1 2 3   (o R1 R and R are as defined in the pre-   ambule) or an alkali metal salt thereof with a benzoic acid derivative of the general formula V o I C-OR 5 / C-CH 5 Z. _R4! -OR (V   (o R and R are as defined in the   preamble <at Z represents a halogen).   10. Process for the preparation of phenoxy-benzoyl-milonates of general formula I (where R1 represents a halogen, cyano, nitro, methylthio, trifluoromethyl or C1-C4 alkyl; R2 and R3 may be the same or different and represent a hydrogen, halogen or trifluoromethyl;   R4 represents hydrogen, halogen, cyano or nitro and R5 represents   has a C1 to C4 alkyl which may be similar to   in which a phenoxy acid derivative is reacted   benzoic compound of the general formula II (where R1, R2, R and R are as defined in the preamble of the present claim and   Y represents a halogen, cyano, ethoxycarbonyloxy or tert.bu-   toxycarbonyloxy) with a metal derivative of a malonic acid ester of the general formula III (where R 5 is as defined in the preamble of the present claim) 11. A process for the preparation of a herbicidal composition   according to any one of claims 5-8 in which 1 2 3 4   mixing a compound of the general formula I (o R, R, R and R and R are as defined in claim 5 in an amount of 0.01-95% by weight with suitable inert solid or liquid carriers and / or diluents and possibly with other auxiliary agents.   12. A method of controlling weeds in the   which one applies on the objects to be protected - preferably on   plants, parts of the plant or the soil - an effective amount   of a compound of general formula I or a composition comprising a compound of general formula I.