NO810798L - OKSIMESTERE. - Google Patents

Description

The present invention relates to oxymester with the general formula *

where R, means hydrogen, alkyl with 1r-6 carbon atoms or

cycloalkyl with 3-6 carbon atoms, R2hydrogen, alkyl with 1-6 carbon atoms, alkenyl with 2r--6 carbon atoms or alkyn-, yl with 2-6 carbon atoms, or R, and R2 form together with the carbon atom they are linked to a cyclopentane- or cyclo^hexane ring, which may optionally be mono-<-, di- or tri*-substituted with alkyl with 1-3 carbon atoms, and R^ is hydrogen, halogen or nitro, with the proviso that R^ and R 2 do not simultaneously mean hydrogen.

The invention further relates to a method for the preparation of compounds of formula I, premergency and postemergency. gency herbicides, methods for the production of such agents and their use, as well as the use of such herbicides as such.

The procedure for preparing compounds of formula

In is characterized by man

a} reacts an acid with formula

■where R 3 has the meaning given in formula I, ! , or a reactive derivative of such an acid with an oxime<;><1>in which R^ and R2 have the meaning given for formula I, or b) reacts a compound with the general formula;<1> jwhere Z means chlorine, bromine, iodo, mesyloxy. or tosyloxy and R, and R„ has the formula..In the sense indicated, I 1 with a compound of the general formula

where R^ has the meaning given above,

or an alkali metal salt thereof in the necessary presence of a base.

The expression "alkyl" with 1-3, respectively lr-3 carbon atoms include, when not stated otherwise - both straight-chain and branched hydrocarbon residues with 1-6, respectively. 1-3 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert.-, butyl etc.

The terms "alkenyl" and "alkynyl" with 2-6 carbon atoms or include unsaturated straight-chain and branched hydrocarbon residues; with up to 6 carbon atoms, such as allyl, butenyl, isobutenyl, ipentenyl, isopentenyl and the like. as well as propargyl, butynyl, isoby-<1>

tinyl et al.

in

i By "halogen" is meant fluorine, chlorine, bromine and iodine, whereby chlorine and iodine are preferred. !

Preferred compounds of formula I are those in which R1 and R„ mean alkyl radicals with 1-2 carbon atoms, especially methyl\,

log R-, hydrogen or chlorine.!

Particularly preferred compounds of formula I are acetone 0-(2-[p-(p-iodophenoxy)phenoxy]propionyl)-oxime and cyclopropylmethyl ketone 0-(2-[p-iodophenoxy)phenoxy]-propionyl oxime, acetone-O-[2-[p-(2-chloro-4-iodophenoxy)-phenoxy]propionyl/-oxime especially the <:>1 Dr isomers of these compounds.

i i Further interesting compounds of formula I are 2-butanone-O-(2-[p-iodophenoxy)phenoxy]propionyl/-oxime; 3-pentanone-O/2-[p-(p-iodophenoxy)phenoxy]propionyl/-oxime; 3-heptanone-O-(2-[p-(p-iodophenoxy)phenoXy]propionyl)-oxime; (2-methyl-2-penten-4-one)-O-(2-tp-(p-iodophenoxy)-penoxy]propionyl)-oxime; diisopro-, pylketone-O-(2-[p-(p-iodophenoxy)phenoxy]propionyl)-oxime; 6-! undecanone-O-[2-(p-(p-iodophenoxy)phenoxy]propionyl oxime; isopropylethylketone-O-[2-tp-(p-iodophenoxy)Penoxy]propionyl oxime;

isobutyl ethyl ketone-0-(2-[p-(p-iodophenoxy)phenoxy]propionyl) oxime; cyclopentanone-O-[p-(p-iodophenoxy)phenoxy].propionyl/-oxime; cyclohexanone-0-/2-[p-(p-iodophenoxy lphenoxy]propionyl/-oxime; 2,3,3-trimethylcyclohexanone-0-/2-[p-(p-iodophenoxy)-phenoxy]propionyl/-oxime, especially the corresponding D isomers.

In one embodiment of the method for preparing a<y>substituted pentoxyalkanecarboxylic acid oximesters with the general formula I, an acid with formula is reacted. II or jet 1 reactive derivative thereof with an oxime of formula III.

The term "reactive derivative of the acid" means above all an acid halide, especially the chloride, or an acid anhydride.

; For the preparation of the substituted phenoxyalkanecarboxylic acid oximester with the general formula I, the esterification of the acid with the general formula II or the acid derivative is carried out. with oxime of the general formula III preferably in a suitable solvent with temperatures from about -10 to +10°C. i Especially preferred is + 20 to + 7 0°C. When using an acid halide as a reactive derivative of the acid, the reaction with the oxime is suitably carried out at room temperature and in mild weather by an acid acceptor, e.g. a tertiary amine, such as pyridine or triethylamine or in alkaline solution according to Schotten-Baumann. A higher yield is obtained than the corresponding ester.

As acid halide, the acid chloride is preferred. Reaction is preferably carried out in the presence of an inert solvent such as benzene, toluene, petroleum ether or according to Schotten-Baumann, i ; alkaline solution. In the application of anydride of the acid with j ; the general formula II, the corresponding oximester of the general formula I can be prepared in high yield by heating the anhydride with the oxime of the general formula<1>III in the presence of a base, preferably an alkali metal carbonate. Particularly preferred is sodium carbonate.

When the free acid of formula II is used as starting material, this is reacted with the oxime of formula III in the presence of dicyclohexylcarbodiimide. For this purpose, the acid of formula II is suspended in an inert organic solvent such as a chlorinated hydrocarbon, e.g. dicormethane, chloroform, carbotetrachloride or trichloroethane, an ether such as e.g. diethyl ether, diisopropyl ether or dioxane, and then the oxime of formula III is suspended in this mixture. The dicyclohexylcarbodiimide is suitably dissolved in the same solvent and added to the reaction mixture. The reaction can take place in a temperature range between 0° and the boiling temperature of the reaction mixture, preferably between room temperature and 50°C. After approx. 2 hours

the reaction is finished, the reaction mixture is filtered and then evaporated. The residue is optionally recrystallized for purification or chromatographed.

; In a further embodiment for the preparation of compounds of formula I, a compound of formula IV is reacted with a ! compound of formula V or an alkali metal salt, in particular; sodium or potassium salt, in a manner known per se. i The reaction conveniently takes place in an inert organic solvent such as hydrocarbons, e.g. benzene or toluene, ethers, e.g. diethyl ether, tetrahydrofuran, dimethoxyethane

or hexamethylphosphoric acid triamide, etc. Temperature and pressure

, is not critical, and one preferably works at a temperature between -20°C and the reflux temperature of the reaction mixture, preferably between -10° and 30°C.

The compounds with the general formula I also include optical isomers, as they have an asymmetric carbon atom in the -1 position. Further asymmetric carbon atoms can be contained in the ester-j components. If desired, the racemic compounds are dissolved into dextrorotatory and levorotatory compounds using known methods. Such methods are e.g. described in Industrial and Engineering Chemistry '6_0 (8) 12-28. The isomers and the racemic mixtures all have herbicidal activity, but the degree of this activity

is different. The activity of the D isomers is strongest. Then follows the racemic mixture and then the L-isomer,<!>

In the context of such investigations, it was found that

e.g. in certain experimental devices, the D-isomer of acetone-O-/2-[p--(p-rhodophenoxy)phenoxy]-propionyl/-oxime shows a greater activity than the racemic mixture. The D-isomers of the compounds of formula I are therefore preferred.

The isomers - especially the D-isomers -■ can also be produced, by synthesis of corresponding optically active starting materials•

,As a result of the nitrogen-carbon double bond i

<!> group, you always get two geometric isomers (when R, and '

] R 2 has different meanings), which are denoted as syn-I and antiform. In certain cases it is possible to isolate such isomers. This is also the subject of the invention.} ! ji 'i: The present invention also relates to herbicidal mixtures, which contain one or more compounds of formula I I as defined above as active ingredient. The herbicidal mixture suitably contains at least one of the following materials: carrier, wetting agent, inert diluent,<1>agent and solvent. !

The compounds of formula I according to the invention are distinguished

compared to known compounds with a similar structure with essentially the same herbicidal effect through significantly better tolerability towards useful plants, e.g. wheat or|sugar beet.\i-

The preemergency and postemergency herbicides according to the invention are particularly suitable for the control of weeds, in particular

ialopecurus myosuroides and millet species such as e.g. echinochloa crus-galli, setaria faberii and panicum capillare in cereals, especially barley, oats and wheat as well as rice, cotton, soya, in sugar beet and vegetable crops. The preemergency and postemergency herbicides according to the invention are particularly preferred for the control of weeds in sugar beet cultures. Thus, e.g. acetone-0-/2-[p-(p-iodophenoxy)phenoxy] propionyl/-oxime at a concentration of 1.25 kg/h sufficient action against weeds without nevertheless damaging sugar beet cultures. In general, a concentration of 0.3-2.kg/h is 'enough, preferably 0.5-1.0 kg/h, especially 0.8 kg/h, to'

achieve the desired herbicidal effect with compound in formula 1.<1>ii' 1

in

Compounds of formula I are generally water insoluble and can be formulated according to one of the usual methods for insoluble compounds.

I I

If desired, the compounds of formula I can be dissolved in a water-immiscible solvent such as e.g. a high-boiling hydrocarbon, which conveniently contains dissolved emulsifiers; dry, so that when water is added it acts as a self-emulsifiable oil.

IN

The compounds of formula I may also be mixed with a wetting agent with or without an inert diluent to form a wettable powder, which is soluble or dispersible in water, or they may be mixed with the inert diluent to form a solid or powdery product .

■Inert diluents such as the compounds of formula I

can be treated with, are solid inert media, incl. powder-! shaped or finely divided solids such as e.g. stoneware, sand, talc, mica, fertilizers etc., as such products are either available as dust or as material with larger particle sizes.

The humectants can be anionic compounds, such as e.g. soaps, fatty sulfate esters, such as dodecyl sodium sulfate, octadecyl sodium sulfate and cetyl sodium sulfate, fatty aromatic sulfonates such as alkylbenzene sulfonate or butyl naphthalene sulfonates, complex fatty sulfonates, such as amide condensation products of oleic acid and N-methyltaurine or sodium sulfonate of dioctyl succinate.

The conditioners can also be non-ionic wetting agents such as e.g. condensation products of fatty acids, fatty alcohols or fat-substituted phenols with ethylene oxide, or fatty acid esters and ethers of sugar or polyhydric alcohols or the products obtained from the latter by condensation with ethylene oxide, or the products known as block polymers of ethylene oxide and propylene oxide. The humectants can also be cationic agents such as e.g. cetyltrimethylammonium bromide, etc.

The herbicidal mixture can also be in the form of an aero-i.. r sol compound, where, in addition to the propellant gas, which is expediently a polyhalogenated alkane such as j in dichlorofluoromethane, a carbon solvent and a

* in moisturizer.

in

The herbicidal mixtures according to the present invention can (in addition to the compounds of formula I) contain synergists and other active insecticides, cathericides, herbicides and fungicides.

In its different areas of application, the compound according to the invention can be used in different amounts.

.The herbicidal agents according to the invention can be present in a

! in a form that makes them suitable for storage and transport. Such !<1>

shapes can e.g. contains 2-90% of one or more active; substances of formula I. These forms can then be diluted with the same or different carrier materials up to concentrations suitable for practical use. In ready-to-use products, there may be active ingredient concentrations of 2-80%

in (weight percent). The active substance concentration can nevertheless also be lower or higher. Depending on the intended use

an active ingredient concentration of 2-8% is preferred, respectively 25-50% : especially.

Valuable starting materials for the preparation of the compound ices of formula I are compounds of general formula

where R means hydrogen or alkyl with 1-6 carbon atoms and in 'R^ hydrogen, halogen or nitro. i i ' The formula II a thus includes acid with formula II and also the corresponding C 1 -C 8 alkyl esters, which through saponification can be transferred into the free acids. i i Particularly preferred compounds of formula II a are<1>i 1 [p-(p-iodophenoxy)phenoxy]-propionic acid and 2-(p-iodophenoxy)phenoxy]'-propionic acid ethyl ester, 2-tp-(2-chloro-4 -iodophenoxy)phenoxy]-!propionic acid and 2-[p-(2-chloro-4-iodophenoxy)phenoxy]-propionic acid-I ethyl esters, especially the D-isomers of these compounds. M The starting materials of formula IIa stated above are new compounds in the form of their D-isomers. They are also valuable as herbicides, as they have a similar activity. spectrum as compounds with formula I. They have the advantage that, in comparison with the individual racemate, e.g. have a . lower phytotoxicity than on cotton and soybeans. These new D isomers of formula IIa are likewise a subject of prior invention.

The starting materials of formula V and II can be prepared according to the following reaction core:

Below, the p-phenoxyphenyl benzoate under formula VI is either reacted with iodine monochloride in aqueous acetic acid or treated with potassium iodide and an oxidizing agent, e.g. potassium iodate or hydrogen peroxide in aqueous methanol, obtaining iodine derivative with formula VII. This is saponified by heating in lye (e.g. alcoholic sodium hydroxide) to p-(p-iodophenoxy)-phenol VIII.

in 1

in i

i , When treating the compound VIII or a corresponding<;>

alkali metal phenolate with a lactic acid alkyl ester tolyl sulfonate, e.g. the corresponding ethyl ester (R=ethyl), one comes across the intermediately formed compound with formula IX to i

reads under Ila, as through treatment with Claisen liquor! I to free acid II can be saponified. When an optically active lactic acid alkyl ester tolylsulfonate is used below, an optically active ester Ila and an optically active acid II are obtained. D(+)-acid II. j

The following examples will illustrate it. present j invention. All temperatures are given in °C. j.

' : j EXAMPLES

Example 1

1.1 g of a 50% suspension of sodium hydride in mineral oil are washed twice in a nitrogen atmosphere with 5.0 ml tetrahydrofuran, introduced into 15.0 ml tetrahydrofuran and mixed dropwise in a solution of 7 g p-(p- iodophenoxy)phenol, dissolved in 30.0 ml: dimethylformamide.

in

in

Finally, 5.2 g of 2-bromopropionyl-> in acetonoxime in 20.0 ml of dimethylformamide are dripped into the mixture. !

The reaction mixture is heated for 2 hours under reflux conditions, then cooled, poured onto ice and extracted exhaustively with ether. The ether extract is washed with water, dried over sodium sulphate and evaporated under reduced pressure.

■ The remaining acetone-0-(2-[p-iodophenoxy)-phenoxy]-propionyl/,

-oxime can be purified by adsorption on silica geljn20.5887

'D

I The p-(p<-iodophenoxy)-phenol used below as starting material can be prepared as follows: A solution of 290.4 g of p-phenoxyphenylbenzoate in 1400 ml of glacial acetic acid is heated with stirring to the boiling point. For this, drip over the course of 10 minutes. a solution of 340 g of iodine monochloride in 800 ml of glacial acetic acid. 1800 ml of boiling water is then added and the mixture is stirred for 2 hours at 95°-100°C. Finally, the mixture is cooled once more with 1800 ml of boiling water to 20°<:>during which p-(p-iodophenoxy)-phenylbenzoate crystallizes out,

in

After adding 1000 ml of a 10% sodium hydrogen sulphite solution, the crystallisate is filtered off and washed with 1000 ml of diluted acetic acid and 2000 ml of salt-free water. !The product is recrystallized from acetic ester-n-hexane (1:4), 'Melting point: 121-124°.

300 g of the thus obtained p-(p-iodophenoxy)-phenylbenzoate are suspended in 2800 ml of 96% ethanol, mixed with 700 g

<1>20% sodium hydroxide solution and heated for 90 min, at j

the boiling water bath. The alcohol is then distilled off, the azeotrope mixture and the residue is mixed with 1500 ml of salt-free water. After adding 380 ml of concentrated hydrochloric acid, extract 3 times with 1500 ml of dichloromethane each time. 'in ; j

. The methylene chloride extract is washed twice with 500 ml of saturated sodium bicarbonate solution each time, 2n hydrochloric acid and salt-free water, dried over sodium sulphate and . evaporated to 500 ml under reduced pressure. After the addition of 500 ml of hot n-hexane, 201.0 g of p-(p-iodophenoxy)_phenol are obtained, with a melting point of 119-121°. !

Example 2

In an analogous way as in example 1, reaction of 2-bromopropionylcyclopropylmethylketonoxime with p-(p-iodophenoxy\-1 phenol cyclopropylmethylketone-0^/2- [p-(p-iodophenoxy)phenoxy]-propionyl/^oxime ;

20

:n : 1,588.

D

' Example 3

4 g of D-2-'tp-(p-iodophenoxy).phenoxy]propionic acid and 0.76 g of acetonoxime are dissolved in 40 ml of methylene chloride. A solution of 2.14 g of dicyclohexylcarbodiimide in: 15 ml of methylene chloride is added drop by drop at room temperature over the course of 5 minutes. It is stirred for a further 1 hour at room temperature, and the precipitated N,N'-dicyclohexyl urea is filtered off.

The filtrate is poured into water and extracted with 200 ml of methylene chloride. The extract is dried over sodium sulfate and evaporated under reduced pressure. The remaining acetone-0-/2-D^[p-(p-' iodophenoxy)phenoxy]propionyl/-oxime can be purified by adsorption on 10 times the amount of silica gel, ;

in !

in i

.Yield:<73>,<2%><n20>^ +35f44<o>(c=lf97% in CHCl^)

The following as starting material used D-2-tp-(-iodo- i

Phenoxy]propionic acid can be prepared as follows: To 134.6 g of sodium p-(p-iodophenoxy)phenolate in 500 ml; Dimethylformamide drops at room temperature 109.1 g ! L-(-)-Lactic acid ethyl ester tolyl sulfonate dissolved in 300 ml \

dimethylformamide. It is stirred for a further hour and poured in

In 1000 ml of water. The product is extracted with 2 x 500 ml of ethyl acetate. The organic phase is washed again with 500 ml of salt-free water, dried over sodium sulphate and evaporated under reduced pressure. The residue crystallizes from n-hexane at -20°. You get

127.1 g D(+)-2-[p-(p-iodophenoxy)phenoxy]-propionic acid ethyl ester. i Melting point: 48-51°; a<22>: 16.88 (c=1.84% in CHCl3) j j

D

121 g of the thus obtained ethyl ester are dissolved in 200 ml of 1 methanol. Add 71.4 ml of Claisen liquor quickly to this.

Below that, the temperature rises to 40°. It is stirred for an hour at room temperature, then the whole is poured into 1000 g of ice1

■ and acidify with 300 ml of 2N hydrochloric acid. The product is extracted with 1000 ml of ethyl acetate. The organic phase is washed neutral with 3 x 500 ml salt-free water, dried over sodium sulfate and distilled off under reduced pressure.

After recrystallization from methylene chloride/n-hexane (1:2), 93.6 g of D(+)-2-tp-(p-iodophenoxy)phenoxy]-propionic acid is obtained. Melting point: 121-124°; aD<22>: 13.03 (c=1.82% in CHCl-.) .

in Example 4 ■

■5.0 g D-2-[p-(2-chloro-4-iodophenoxy)phenoxy}-propionic acid and 0.9

1g'acetone oxime is placed in 70.0 ml of dichloromethane. Now added

while stirring, an addition of 2.5 g of N,N-dicyclohexylcarbodiimide in 30.0 ml of dichloromethane and stirring for a further hour. Then

filtered and washed with 10 ml of ether. The solvent is evaporated and the residue is filtered through 10 times the amount of silica gel. c*

(Eluent: Hexane/ethyl acetate, 9:11. One obtains •acetone-0-/2-D-[p-(2-chloro-4-iodophenoxy)phenoxy]propionyl/- ; ; 1 oxime; [a]<20 >+ 34.97 u o (c=1.38% in chloroform). can be produced as follows;

in

il a 2.5 1 S-flask with stirrer, thermometer, dropping funnel ; j and cooler, 269.5 g of hydroquinone and 90.6 g of calcium hydroxide are placed in 1224 ml of dimethyl sulphoxide. A solution of 235.0 g of 3,4-dichloronitrobenzene in 367 ml of dimethylsulfoxide is then added while stirring and further stirred at 80°. Then acidify with: 800 ml of hydrochloric acid 2N to pH1 and extract three times with 800 ml of ethyl acetate. The ethyl acetate phase is washed with 800 ml of sodium bicarbonate and 800 ml of water. After drying over sodium sulfate, the solvent is evaporated. The evaporation residue is recrystallized from alcohol/water (1:1). p-(2-chloro-4-nitrophenoxy)-phenol with a melting point of 15 2° is obtained.

In a 1.5 liter S-flask, 110 g of the thus obtained p-(2-chloro-4-nitro4enoxy)rf enol are heated together with 9.4 g of activated carbon and 5.4 g of iron III chloride in 68 0 ml methanol with reflux. Within 30 min. 33.0 g of hydrazine hydrate are added dropwise while stirring. Stirring is continued at reflux for 20 hours, then cooled, filtered and the solvent evaporated.

The residue is taken up in 400 ml of ethyl acetate, insoluble parts are filtered off and the phenol is combined with 400 ml of n-hexane and the product is crystallized out. One obtains p^(4-amino-2-chlorophenoxylphenol.

In a 250 ml S-flask, 5.4 g of iodine and 6.0 g of isopentyl nitrile are placed in 100 ml of acetonitrile and the mixture is heated to 65°. Then a solution of 10.0 g is added dropwise; p-(4-amino-2-chlorophenoxy)iphenol in 50 ml of acetonitrile slowly with stirring. The mixture is then stirred at 65° for 20 min. The reaction mixture is then poured onto 200 g of ice, extracted 3 times with 200 ml of ethyl acetate, washed twice with 200 ml of saturated sodium thiosulphate solution and twice with 200 ml of water. ; After drying over sodium sulfate, the solvent is evaporated, the residue is filtered through 10 times the amount of silica gel (eluent: hexane/ethyl acetate, 9:1). 12 g of the thus obtained p-(2-chloro-4-iodophenoxy)phenol• are dissolved in 100 ml of dimethylformamide. During cooling, 0.83 g of sodium hydride is added. After complete hydrogen evolution, a solution of L-(-)-lactic acid ethyl ester tolylsulfinate, I i; 50 ml of dimethylformamide slowly and it is stirred for 1 hour at room temperature. The reaction mixture is then poured into 500 ml of water, extracted three times with 500 ml of ethyl acetate, twice with 150 ml of caustic soda 2N and washed neutral with

in 600 ml of water. After drying over sodium sulfate, the solvent is evaporated. The residue obtained is filtered through 10 times the amount of silica gel (eluent: hexane; finally hexane/ethyl acetate 9:1). 2-D-[p-2-chloro-4- is obtained.

i 2 0 o ' • iodophenoxy)phenoxy]-propionic acid ethyl ester; [a] +15.03 '■

(c=1.57% in CHCl 3 ). D

In a 200 ml S-flask, heat 8.8 g of the 2-D-[p-(3-chloro-4-phenoxy)phenoxy]-propionic acid ethyl ester thus obtained and

; 6 ml of Claisen liquor in 100 ml of methanol while stirring at reflux, then stir for a further 1 hour. The reaction mixture is then acidified with 100 ml of hydrochloric acid 2N to pH1, extracted 3 times with 150 ml of ethyl acetate and washed neutral with 600 ml of water. After drying over sodium sulfate, the solvent is evaporated.

The residue obtained is filtered through 10 times the amount of silica gel. (Eluent: hexane/ethyl acetate; 7:3). ^2-D-[p-(2-chloro-4-iodophenoxy)phenoxy]-propionic acid is obtained:

[a]<20>+8.89° (c=1.61% in chloroform).

: D

Example 5

In an analogous manner to example 3', reaction of D-2-[p-(p-iodophenoxy)phenoxy]propionic acid with cyclopropylmethyl ketone oxime gives cyclopropylmethylketone-0-(2-D-[p-(p-iodophenoxy) phenoxy! propionyl/-oxime; n<20>: 1.5866; « +43.05 (c=1.56% in CHC1 )

: D 3;

Example 6 'I

In an analogous way to examples 1-4, the following compounds can | produced: i

j 2-butanone-O-(2-D-tp-(p-iodophenoxy)phenoxy]propionyl/-o:xime;

■a^ = +46.6 , n^ = 1.5832 i : ! YOU t! 14-heptanone-O-(2-D-[p-(p-iodophenoxy)phenoxy]propionyl)-oxime;

<a<22>= +50.25°, n20 = 1.5666 j d

j(2-methyl-2-penten-4-one)-O-D-[p-(p-iodophenoxy)-phenoxy]-propionyl/-oxime; ct22 = +46.96°, n20 = 1.5880

DD

;Diisopropylketone-O-(2-D-[p-(p-iodophenoxy)phenoxy]-propionyl)rioxime; +44.1°,T^=J-'5660

16-undecanone-O-(2-[p-(p-iodophenoxy)phenoxy]propionyl)-oxime;

a<22>= +48.09°, n20 = 1.5496

Isopropyl ethyl ketone-O-[2-D-[p-(p-iodophenoxy)phenoxy]-propionyl/-oxime; a<22>= +51.46°, n<20>= 1.5703

Isobutyl ethyl ketone-0-(2-D-[p-iodophenoxy)phenoxy]-propionyl/- in oxime; a22 = + 50.64°, n20 = 1.5652

in

;Cyclopentanone-O-(2-D-[p-(p-iodophenoxy)phenoxy]propionyl) oxime; a = +46.2 .

D

Cyclohexanone-O-(2-D-[p-(p-iodophenoxy)phenoxy]propionyl)-oxime;

a<20>= +49.4°, n20 =1.5802

4- methyl-3-pentanone-0-(2-D-[p-(p-iodophenoxy)phenoxy]-propionyl)

2 0 , r, .ro 2 0 , ,- „ 0 -oxime; aD = +51.46 , nQ =1.5703 5- methyl-3-hexanone-0-/2-D- [p- (p-iodophenoxy).phenoxy] -propionyl/- 20 ,cn r a°20 crc„ , oxime; aD = +50.64 , nD = 1.5652. Example 7 in '<<>, For the production of an emulsifiable concentrate, the subsequently listed components of this concentrate are mixed with each other; In i

While mixing, bring up to 1 1 with xylene.

Claims (21)

in 1. Compounds characterized by the general formula in where means hydrogen, alkyl with 1-6 carbon atoms or I cycloalkyl with 3-6 carbon atoms, R„ hydrogen, alkyl with 1-6 • carbon atoms, alkenyl with 2-6 carbon atoms or alkynyl with 2-6 carbon atoms, or R^ and R2 form together with carbon atoms they are linked to a cyclopentane or: cyclohexane ring, which may optionally be mono-, di- or tri-substituted with alkyl with 1-3 carbon atoms, and R^ is hydrogen, halogen or nitro, with the proviso that and R2 not at the same time, means hydrogen. 2. Compound with formula I according to claim 1, characterized in that R.^. and R 2 means alkyl residues with 1-2 carbon atoms and R 2 hydrogen or chlorine. 3. Compound with the general formula I according to claim 1, characterized in that R 1 and R 2 mean a methyl group and R 1 hydrogen or chlorine. in 4. Acetone-O-(2-[p-(p-iodophenoxy)-phenoxy]propionyl) oxime. Cyclopropylmethylketone-O-[2-[p-(p-iodophenoxy)-penoxy]propionyl; /-oxime. in in in 6. Acetone-0-(2-[p-(2-chloro-4-iodophenoxy)phenoxy)pro pionyl/-oxime. ; i i' 7. Optically active compounds of the D series corresponding to compounds according to claims 1-6. in . 8. Compound according to one of claims 1-7 as herbicide. 9. Herbicidal agents, characterized in that it contains at least one compound with the general formula I i where R means hydrogen, alkyl with 1-^ 6 carbon atoms or i cycloalkyl with 3-6 carbon atoms, R2 hydrogen, alkyl with 1-6 carbon atoms, alkenyl with 2-6 carbon atoms or alkynyl with 2-6 carbon atoms or R1 and R2 forms together with the carbon atom to which it is attached a cyclopentane or cyclohexane ring, which may optionally be mono-, di- or tri-substituted with alkyl with 1-3 carbon atoms, and R^ is hydrogen, halogen or nitro, with the proviso that R^ and R2 not at the same time; means hydrogen, and inert carrier material. 10. Herbicides according to claim 9, characterized in that it contains acetone-O-[2-[p-(p-iodophenoxy)-phenoxy]propionyl/-oxime. in 11. Herbicides according to claim 9f . characterized in that they contain 1-acetone-O-/-2-[p-(2-chloro-4-iodo-phenoxy)phenoxy]-propionyl/-i oxime. in 12. Herbicides according to claim 9, characterized in that they contain cyclopropylmethylketone-O-[p-(p-iodophenoxy]-propionyl) oxime. 13. Herbicides according to one of claims 9-12, characterized in that they contain the D-isomer of compound of formula I. , t 14. Procedure for the preparation of compounds with the general formula: where R^ means hydrogen, alkyl with 1-6 carbon atoms or cycloalkyl with 3-6 carbon atoms, R2 is hydrogen, alkyl with 1-6 carbon atoms, alkenyl with 2^ 6 carbon atoms or alkynyl with 2-6 carbon atoms, or R1 and R2 together with the carbon atom, they are bonded to form a cyclopentane or cyclohexane ring which may optionally be mono-, di- or tri-substituted with alkyl with 1-3 carbon atoms, and R^ is hydrogen,' halogen or nitro, with the proviso that R^ and R2 do not at the same time means hydrogen, characterized by the fact that one a) reacts an acid with formula i i ■• ! 1 : ; i i 'where R-. has the meaning given in formula I, or a reak-..'. tive derivative of such an acid, with an oxime ,hyor R^ and R2 have the meaning given for formula I, orb) reacts a compound with the general formula where Z means chlorine, bromine, iodine, mesyloxy or tosyloxy and R 1 and R 2 have the meaning given for formula I, , with a connection of the general formula where R 3 has the meaning given above, I: or an alkali metal salt thereof, if necessary in the presence j low a base. IN 15. Method according to claim 14 in the production of; In i , ; acetone-O-/2-[p(p-iodophenoxy)phenoxy]propionyl/-oxime, J characterized by reacting (p-iodopheno-]j xy)phenol with 2-bromopropionylacetone oxime. in j. 1! , 16. Method according to claim 14 for the production of acetone-0-/2-[p-(p-iodophenoxy)phenoxy]propionyl/-oxime, characterized in that one reacts 2-[p-: (p-iodophenoxy)-phenoxy] propionic acid in the presence of dicyclohexylcarbodiimide with acetonoxime. ! in 17. Process according to claim 14 for the production of acetone-O-[2-[p-(2-chloro-4-iodophenoxy)phenoxy]propionyl/-oxime, in characterized by converting 2-[p-(2-chloro- .4-iodophenoxy)phenoxy]propionic acid in the presence of dicyclohexyl- : ; carbodiimide with acetonoxime. 18. Method according to one of claims 14-17, characterized in that starting materials are used which lead to D isomers of the compound of formula I. 19. Procedure for combating weeds, characterized by treating them with one of the agents mentioned in claims 9-13. 1 20. Use of the compounds mentioned in claims 1-7 as a weed control agent. 21. Compounds with the general formula characterized by the above-mentioned formula where R means hydrogen or alkyl with 1-6 carbon atoms and R^ hydrogen, halogen or nitro in the D form. in 1 in 22. 2-D-[p-(p-iodophenoxy)phenoxy]-propionic acid. 23. 2-D-[p-(p-iodophenoxy)phenoxy-propionic acid ethyl ester. 24. 2-D-[p-(2-chloro-4-iodophenoxy)phenoxy]-propionic acid.. .25. 2-D-[p-(2-chloro-4-iodophenoxy). phenoxy]-propionic acid ethyl ester.