NO149351B - PROPIONIC ACID ESTERS AND HERBICIDE AGENTS CONTAINING SUCH - Google Patents

Description

The present invention relates to connections with it

general formula

where R means hydrogen, alkyl with 1-6 carbon atoms or phenyl, R 2 alkyl with 1-6 carbon atoms, alkanyl with 2-6 carbon atoms, bone atoms, alkynyl with 2-6 carbon atoms or phenyl, or in 12

R and R form together with the carbon atom to which they are attached

a cycloalkane ring with 4-10 carbon atoms, which may optionally

be mono-, di- or tri-substituted with alkyl with 1-3 car-<1>

3 4 bon atoms, R is halogen, trifluoromethyl or nitro and R

and R<5> is hydrogen or halogen as racemate and as opt■<->

isomers.

The invention further relates to herbicidal agents which contain compounds of formula I (preemergency or postemergency). • - j i ti

Also the German Offenlegungsschrift 2.22 3.894 describes

blue. alkyl esters of 2-phenoxyphenosky-propionic acids which

suitable as herbicides. The connections according to up-

the invention differs from the known mainly in that they have a ylideneaminooxy substituent on the alkyl group. This structural difference is believed to be the cause of the strong

er herbicidal activity compared to the known for-

bonds.

The compounds according to the invention with formula I can produce

is posed by that one

Tr -

a) reacts a salt of an acid with formula ,\

3 4 5 where R , R and R have the meanings given in formula I: with a compound of formula 1 2 'where R and R have the meanings given in formula I and X means a leaving group, or in b) reacts a compound of formula

in

• 1 2

, where Z- means a leaving group and R and R have the meanings given for formula 1 I,

with a compound of formula

3 4 5

where R , R , and R have the meanings given for formula I, or an alkali metal salt thereof, if necessary in the presence of a base, or

c) reacts a compound of formula

wherein R<b> denotes a lower alkyl, aryl or heteroaryl group and R , R and R have the meaning given for formula I, with a compound of formula

1 2

where R and R have the meaning given for formula I,

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

The term "alkyl" with 1-6 respectively 1-3 carbon atoms includes - 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, iso-butyl , tert.-butyl and the like. The term "lower alkyl" is to be understood in particular as alkyl groups with 1-6 carbon atoms.

The terms "alkenyl" and "alkynyl" with 2-6 carbon atoms include unsaturated straight-chain or branched hydrocarbon residues with up to 6 carbon atoms such as allyl, butenyl, iso-butenyl, pentenyl, isopentenyl and the like as well as propargyl, butynyl, isbutynyl, pentinyl and the like. Particularly preferred alkynyl groups are 1-propynyl, butynyl and isobutynyl.

The term "halogen" includes fluorine, chlorine, bromine and iodine, preferably chlorine, bromine and iodine.

The cycloalkane ring preferably contains 4-7 carbon atoms, especially 4-6 carbon atoms.

Under "aryl groups" is meant in particular phenyl, optionally substituted 1-3 lower alkyl groups, as well as naphthyl. The alkyl groups can be the same or different.

Preferred "heteroaryl radicals" are the pyridyl, imidazolyl, thiazolyl and thiophenyl radicals.

Preferred compounds of formula I are those in which R^" means methyl or ethyl, those in which R 2 means methyl, ethyl or phenyl, those in which R 3 means chlorine or trifluoromethyl, those in which R<4> means hydrogen and those in which R<5> means hydrogen Also the compounds of formula I in which R<1> and R 2 together with the carbon atom to which they are attached form a cycloalkane ring which is optionally substituted with alkyl, are preferred.

Particularly preferred compounds of formula I are: DL-2-[p-[(α,α,α-trifluoro-p-tolyl)oxy]phenoxy]-propionic acid-[[(isopropylideneamino)oxy]methyl]ester; D-2-[p-[(α,α,α-trifluoro-p-tolyl)oxy]enoxy]propionic acid-[[(isopropylideneamino)oxy]methyl]ester; D-2-[p-(p-bromophenoxy)phenoxy]-propionic acid-[[(isopropylideneamino)oxy]methyl]ester; D-2-[p-[ (α,α,α-trifluoro-p-tolyl)oxy]phenoxy]propionic acid-[[(cyclopentylideneamino)oxy]methyl]ester;

D-2-[p-[(α,α,α-trifluoro-p-tolyl)oxy]phenoxy]-propionic acid-

[ [ (cyclohexylidene amino) oxy] methyl] ester;

D-2-[p-[(α,α,α-trifluoro-p-tolyl)oxy]phenoxy]propionic acid-[[(cycloheptylideneamino)oxy]methyl]ester; D-2-[p-[(α,α,α-trifluoro-p-tolyl)oxy]phenoxy]-propionic acid t[(benzylideneamino)oxy]methyl]ester; D-2-[p-[(α,α,α-trifluoro-p-tolyl)oxy]phenoxy]-propionic acid-[[(1,3-dimethyl-2-butenylideneamino)oxy]methyl]ester.

In one embodiment for the preparation of the compound with

in the general formula I, a salt of an acid of formula II is reacted with a compound of formula III.

The term "salt of an acid" means, for example, an alkali metal salt such as a sodium, potassium or lithium salt, or an alkali metal salt such as a magnesium, nesium, calcium or barium salt, a salt of an organic base such as for example a mono-, di- or trialkylammonium salt or a pyridinium salt or the ammonium salt.

The term "leaving group" for X stands, for example, for chlorine, bromine, iodine, tosyloxy, mesyloxy, hydroxyl in free or esterified form, or for one of the following groups:

7 8 9 where R , R and R which residues can be the same or different, means alkyl, especially with 1-6 carbon atoms or two of these also together form a C^^-alkylene group and Y ® an anion, for example a chlorine- , bromine, iodo, hydroxyl or sulfate anion, in which R"*"^ and R^ may be the same or different residues means alkyl, especially with 1-6 carbon atoms, and Y has the above meaning,

12

where R means a lower alkyl, aryl or heteroaryl group and n means 1 or 2.

The esterification of the acid of the general formula II with the compound of the general formula III is preferably carried out in a suitable inert solvent at approx. -10 to 220°C, preferably at room temperature or higher. A particularly preferred temperature range is between 20 and 70° C. The reaction is carried out, for example, in the presence of an inert solvent such as benzene, toluene, petroleum ether, dimethylformamide, tetrahydrofuran, acetonitrile, N-methyl-2-pyrrolidone, tetramethylurea, dimethoxyethane, diglycol dimethyl ether or hexamethylphosphoric acid triamide.

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 of a compound of formula V in a manner known per se.

The term "leaving group" for Z stands for example for one of the leaving groups already specified for X, or for a hydroxy group activated through reaction with triphenylphosphine and azodicarboxylic acid or an ester thereof, especially azodicarboxylic acid diethyl ester (see for example Bull. Chem. Soc. Japan 4_6, 2833 (1973) or Angew. Chem. 88, 111 (1976)).

The reaction according to process variant b) usually takes place in an inert organic solvent such as hydrocarbons, for example benzene or toluene, ethers, for example diethyl ether, tetrahydrofuran, dimethoxyethane or hexmethylphosphoric triamide. Temperature and pressure are 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.

In a further embodiment for the preparation of compounds of formula I, a compound of formula VI is reacted with an oxime of formula VII in the presence of a base, for example an alkali metal carbonate. For this purpose, the compound of formula VI can be dissolved in an inert organic solvent such as a chlorinated hydrocarbon, for example dichloromethane, chloroform, carbon tetrachloride or trichloroethane, an ether or an ether-like compound, for example tetrahydrofuran, diethyl ether, diisopropyl ether, dimethoxyethane or dioxane , an aromatic hydrocarbon, for example benzene, toluene or xylene, dimethylformamide, dimethylsulfoxide or hexamethylphosphoric acid-. triamide, and then the oxime of formula VII is added, preferably in the form of an alkali metal salt. The reaction usually takes place in a temperature range between 0°C and the boiling temperature of the reaction mixture, preferably between 0° and 50°C. After a short time, for example a few minutes, the transaction is normally closed. The reaction mixture is preferably poured onto water and extracted with an organic solvent, for example ethyl acetate. The residue obtained after evaporation is usually recrystallized for purification or chromatographed.

The compounds with the general formula I also include optical isomers, as they have an asymmetric carbon atom in the α-position to the carbonyl group. Further asymmetric carbon atoms can be contained in the ester components. If desired, the racemic compounds can be cleaved using known methods into dextrorotatory and levorotatory compounds. Such methods are described, for example, in Industrial and Engineering Chemistry (H) (8) 12-28. The isomers and the racemic mixtures all have herbicidal activity, but the strength of this activity is different. The most active are the D isomers, followed by the racemic mixture and then the L isomers. In the context of such investigations, it was found that, for example, in certain experimental devices, the D-isomer of 2-/p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-/[(isopropylideneamino) -oxy]methyl]/esters a stronger activity than the racemic mixture.

The isomers can also be produced by synthesis from corresponding optically active starting materials. As indicated above, the D-isomers of the compounds of formula I are particularly preferred and thus also the corresponding starting materials.

As a result of the nitrogen-carbon double bond i

group you always get two geometric isomers (when R 1 and R<2> have different meanings) which are designated as syn- and anti-form. In certain cases it is possible to isolate such isomers. These are also the subject of the invention.

The present invention also relates to herbicides which contain an effective amount of at least one compound of formula I as defined above as a racemate or as an optical isomer. Weed control agents often contain at least one of the following inert materials: Carriers, wetting agents, inert diluents and solvents.

Weed control agents (preemergency and postenergy) according to the invention are particularly suitable for controlling weeds, especially (Alopecurus myosuroides) and millet species such as Echinochloa crus-galli, Setaria faberii and Panicum capillare in cereals - especially barley, oats and rye and rice -, cotton, soya, sugar cane and vegetable cultivation. The preemergency and postemergency herbicides according to the present invention are particularly suitable for controlling weeds in sugar cane cultures. Thus, for example, 2-/p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-/[(isopropylideneamino)oxy]methyl/ester in a concentration of 1.25 kg/hectare sufficient effect against weeds without, however, damaging the sugarcane crops. Generally, a concentration of 0.1-6 kg/hectare, preferably 0.6-2.0 kg/hectare, particularly preferably 1-1.5 kg/hectare is sufficient to achieve the desired herbicidal effect with compounds of formula I.

A comparison with the state of the art gave the following results:

The active ingredient is dissolved in acetone in such a way that a

2% solution of the active substance. Shortly before the beginning of the experiment, it is diluted with water to the desired concentration, which in the present experiment is 600 g/hectare.

The experimental plants (weeds and useful plants) are sprayed in greenhouses with the formulated active substance, the application dosage being 0.6 kg of active substance/hectare at a spray volume of 1000 l/hectare. Using mercury vapor lamps, a 16-hour day is simulated. 18 days after the treatment, the plants are examined with regard to the effect that has occurred, as 100% necrosis means complete destruction of the weed or the beneficial plant.

The results are summarized in the following table.

In the event that R"^ is the trifluoromethyl residue, these compounds can only find conditional use in cereal cultivation, as some phytotoxicity occurs. However, these compounds are particularly suitable for controlling weeds in rice, cotton, soy, sugarcane and vegetable cultures.

The following attempts were made:

The active substance is dissolved in acetone in such a way that a 2 percent solution of active substance is obtained. Shortly before the beginning of the experiment, it is diluted with water containing the wetting agent nonoxynol (condensation product of nonylphenol and ethyleneoxy). The concentration of the wetting agent in the ready-made agent is 0.2% by weight.

The test plants (weeds and useful plants) are sprayed in greenhouses with the formulated active ingredient, at the application dosage 1.25 kg of active ingredient per hectare with a spray volume of 1000 1/ hectare. Using mercury vapor lamps, a 16-hour day is simulated. 20 days after the treatment, the plants are examined with regard to the effect that has occurred, as 100% necrosis means complete destruction of the weed or the useful plant.

The results are summarized in the following table and the names of the examined compounds A-G and I-Q are listed after the table.

They scrutinized connections

Compound A = 2- Cp- \ Jf<,« /=*--trifluoro-p-tolyl) oxyjf enoxy] -

propionic acid-f C(isopropylideneamino)oxy^-methyl} ester

Compound B = D-2-[p- ,-*--trifluoro-p-tolyl).oxy^]f enoxy} -

propionic acid- isopropylideneamino) oxyjme-tyl ester

Compound C-= D-2-fp- [(* <■ ,«,°<--trifluoro-p-tolyl) oxyjf enoxy] -

propionic acid T [(^-methyl-benzylideneamino) oxymethyl] ester

Compound D = D-2-fp-(p-chlorophenoxy)phenoxy]]-propionic acid-E f(isopropylideneamino)oxy]methylj ester

Compound E = 2-fp-(o,p-dichlorophenoxy).phenoxy}-propionic acid-C C(isopropylideneamino)oxy]methyl]ester

Compound F = 2-[p-(o,p-dichlorophenoxy)phenoxyj-propionic acid-fW-methyl-benzylideneaminoJoxyJmethylEster

Compound G = D-2-[p-(p-bromophenoxy)phenoxy-propionic acid-ff(isopropylideneamino)oxyJmethyl]ester

Compound I = D-2-[p-(p-iodophenoxy)phenoxy-propionic acid-TT(isopropylideneamino)oxy]methyl] ester

Compound J = D-2-fp-[>*-,«•<• ,«*--trifluoro-p-tolyl)oxyjphenoxyj-propionic acid- f [(cyclopentylideneamino)oxyjmethylj ester

Compound K = D-2-fp- f(^.,»<-^*.-trif luor-p-tolylJoxy^f enoxy] -

propionic acid- f C(cyclohexylideneamino) oxy^Jmethyl] ester

Compound L = D-2- Ep- f(«J,«:,o<.-trifluoro-p-tolyl) oxy] f enoxyj -

propionic acid- ^(cycloheptyl^61^11^110)oxy]methylJ ester

Compound M = D-2-fp- £(•<,-< ,p<-trifluoro-p-tolyl)oxy Jf enoxyj -

propionic acid-f/T(3,3,5-trimethylcyclohexylidene-amino)oxy]methyl ester

Compound N = D-2-fp- f(<*,«: ^-trifluoro-p-tolyl) oxy] f enoxy] -

propionic acid- f L(benzylideneamino)oxyjmethylj ester

Compound 0 = D-2-fp-f(«*,°<,-<--trifluoro-p-tolyl)oxyjf enoxy] -

propionic acid-/] 0sec. butylideneamino)oxy] methyl ester

Compound P = D-2-fp- |_(^,<-,-«—trifluoro-p-tolyl)oxy Jf enoxyj -

propionic acid-f Q 1-pentyl-hexylideneamino)oxy] methyl ester

Compound Q = D-2-fp-O^^/^-trifluoro-p-tol<y>l)ox<y> Jf enoxyj-propionic acid-TO1•3-dimethyl-2-butenylideneamino)oxyj methylj ester

The compounds of formula I are generally water insoluble and can be prepared by usual methods for insoluble compounds.

If desired, the compounds of formula I can be dissolved in a solvent which is not water-miscible with water, for example a high-boiling hydrocarbon which appropriately contains dissolved emulsifiers, so that when water is added it acts as a self-emulsifiable oil.

The compounds of formula I may also be mixed with a wetting agent with or without an inert diluent for formation

of a wettable powder, which is soluble or dispersible in water, or they can be mixed with the inert diluent to form a solid or powdery product.

Inert diluents with which the compounds of formula I can be treated are solid inert media including powdery or finely divided solids such as clay, sand, talc, mica, fertilizers and the like, as such products can either be present in dust form or as materials with larger particle size.

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

The wetting agents can also be non-ionic wetting agents such as, for example, condensation products of fatty acids, fatty alcohols or fat-substituted phenols with ethylene oxide, or fatty acid esters and ethers of sugars or polyhydric alcohols or the products obtained from the latter by condensation with ethylene oxide, or the products known as block copolymers of ethylene oxide and <p>propylene oxide. The humectants can also be cationic agents such as, for example, cetyl

trimethylammonium bromide and the like.

The weed control agent can also be available in the form of an aerosol, where a carbon solvent and a wetting agent are often used in addition to the propellant, which is a suitable polyhalogenated alkane such as dichlorodifluoromethane.

The weed control agents according to the present invention may, in addition to the compound of formula I, contain synergists and other active substances, for example insecticides, acaricides, bactericides, other herbicides, fungicides, plant growth regulators and fertilisers. Such combination agents are suitable for strengthening the activity or for expanding the spectrum of action.

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

The herbicides according to the invention can be in a form suitable for storage and transport. Such forms can, for example, contain 2 to 90% by weight of one or more active substances of formula I. These formulas can then be diluted with the same or different carrier materials to concentrations that are suitable for practical use. In the ready-to-use agents, the active ingredient concentration can range from 0.05-80% by weight. However, the active ingredient concentration can also be higher or lower. Depending on the intended use, an active ingredient concentration of 2-8 or 50-80% by weight is particularly preferred.

The starting materials with formulas II, III, IV, V and VII belong to known substance classes.

The starting materials of formula VI can be obtained by oxidation, for example with the aid of hydrogen peroxide, of compounds of formula where R3, R4, R<5> and R<6> have the meanings indicated above.

The compounds of formula VI and VIII can be prepared analogously to what is stated in DOS 2,617,804. Racemates obtained in this way can also be split off.

The compounds of formulas VI and VIII where R 1 is a heteroaryl group are new, and regardless of whether they exist as a racemate or in the form of the optical antipodes, for example the D-antipodes. If R<6> in the compounds of formula VI and VIII is a lower alkyl group, for example the methyl group, an aryl residue, for example the phenyl residue or a halophenyl residue, the corresponding D-isomers are likewise new.

These new compounds of formula VI and VIII can, for example, be prepared by reacting the racemate or D-form of a compound of formula II with a compound of formula

This reaction can advantageously be carried out in an inert organic solvent, for example in chloroform or dimethylsulfoxide, and in the presence of dicyclohexylcarbodiimide in a manner known per se. A thus obtained compound of formula VIII can then, for example with hydrogen peroxide, be oxidized to a compound of formula VI.

Particularly preferred starting materials with formulas VI and VIII respectively are:

D-2-[p-(p-bromophenoxy)phenoxy]-propionic acid methyl-thiomethyl ester, D-2-[p-(p-fluorophenoxy)phenoxy]-propionic acid methylthiomethyl ester, D-2-[p -(p-nitrophenoxy)phenoxy]-propionic acid-methylthiomethyl-ester and D-2-[p-(p-trifluoromethylphenoxy)phenoxy]-propionic acid-methyl-thiomethyl-ester respectively the corresponding sulfonyl compounds.

The aforementioned starting materials with formulas VI and VIII, especially the D-forms thereof, are additionally valuable as herbicides, as they have a similar spectrum of activity to the compound of formula 1. They can therefore be used in the same way as described for the compounds of formula I for the production of the herbicidal agents. The D-antipodes have the advantage that, in comparison with the corresponding racemate, for example, they have a lower phytotoxicity on cotton and soybeans.

The following examples shall illustrate the present invention. All temperatures are given in °C.

I. Preparation of active substances with formula I:

Example 1

36 g of 2-β-[(α,α,α-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-[(methylsulfonyl)methyl]ester are dissolved in 20 ml of tetrahydrofuran. To this solution is added a mixture of 0.35 g of acetonoxime sodium salt dissolved in 20 ml of dimethylformamide, and the reaction mixture is stirred for 2 minutes at room temperature. The mixture is poured onto water, extracted with ethyl acetate and washed neutrally with water. The ethyl acetate is evaporated and the residue is then chromatographed on 100 g of silica gel with hexane/ethyl acetate 8:2. The eluate is evaporated and the residue is recrystallized from ether/hexane. The obtained 2-/p-[(α,α,α-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid/[(isopropylideneamino)oxy]methyl/ester melts at 76-77°C. In an analogous manner, by using D-2-/p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-[(methylsulfonyl)methyl]ester and acetonoxime sodium salt, D- 2-/p-[(α,α,α-trifluoro-p-tolyl).oxy]phenoxy/-propionic acid-/[(isopropylideneamino)oxy]methyl/ester; Fp. 80-85°; fa]^<2> +11.62° (c = 1.25% in CHCl 3 ). D-2-/p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-[(methylsulfonyl)methyl]ester and acetophenoxymine sodium salt/ D-2-/p-[(a,a ,α-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-/[(α-methyl-benzylideneamino)oxy]methyl/ester; Fp. 63-64°; [α]22 -13.64° (c = 0.75% in CHCl 2 ). D-2-[p-(p-chlorophenoxy)phenoxy]-propionic acid-[(methyl-sulfonyl) methyl]ester and acetonoxime sodium salt D-2-[p-(p-chlorophenoxy)phenoxy]-propionic acid-/[(isopropylideneamino) oxy]methyl/ester; ri<20> 1.5480; [a]<22> +13.58° (c = 1.93% in CHClg). 2-[p-(o,p-dichlorophenoxy)phenoxy]-propionic acid-[(methylsulfonyl)methyl]ester and acetonoxime sodium salt, 2-[p-(o,p-dichlorophenoxy)phenoxy]-propionic acid-/[(isopropylideneamino )oxy]methyl ester; nQ 1.5557. 2-[p-(o,p-dichlorophenoxy)phenoxy]-propionic acid-[(methylsulfon-yl)methyl]ester and acetophenoxym sodium salt 2-[p-(o,p-dichlorophenoxy )phenoxy]-propionic acid-/[(a -methyl-benzylideneamino)oxy]methyl ester; Fp. 66-67°. D-2-[p-(p-bromophenoxy)phenoxy]-propionic acid-[(methylsulfonyl)methyl]ester and acetonoxime sodium salt/D-2-[p-(p-bromophenoxy)phenoxy]-propionic acid-/[(isopropylideneamino) oxy]methyl/ester; n<20> 1.5593; [a]<22> + 11.92° (c = 1.15% in CHCl 3 ). D-2-[p-(p-iodophenoxy)phenoxy]-<p>propionic acid-[(methylsulfonyl)methyl]ester and acetone oxime sodium salt,D-2-[p-(p-iodophenoxy)phenoxy]-propionic acid-/ [ ( isopropylideneamino).oxy]methyl/ester; Fp. 40.43°; [a]<22> +8.60° (c = 0.90% in CHCl3). D-2-/p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-[(methylsulfonyl]methyl]ester and cyclopentanone oxime sodium salt D-2-/p-[(a, α,α-trifluoro-p-tolyl)oxy]-phenoxy/-propionic acid/[(cyclopentylideneamino)oxy]methyl/-ester, mp 43-45°; [a]<22> +7.52° (c = 2.28% in CHCl3). D-2-/p- [(a,a,a-trifluoro-p-tolyl).oxy]phenoxy/-propionic acid-[(methylsulfonyl)methyl/ester and cyclohexanone oxime sodium salt,D-2-/p< ->[(α,α,α-trifluoro-p-tolyl)oxy]-phenoxy/-propionic acid/[(cyclohexylideneamino)oxy]methyl/-ester; Fp. 71-73°; [a]<22> +5.55° (c = 1.49% in CHCl3). D-2-/p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-[(methylsulfonyl)methyl]ester and cycloheptanone oxime sodium salt-t D-2-/p-t(a, α,α-trifluoro-p-tolyl)oxy]-phenoxy/-propionic acid/[(cycloheptylideneamino)oxy]methyl/-ester; Fp. about. 30°; [a]<22> +6.00° (c = 1.96% in CHCl3). D-2-/p<->[(α,α,α-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-[(methylsulfonyl)methyl]ester and 3,3,5-trimethylcyclohexanone oxime sodium salt, D- 2-[(α,α,α-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-/[(3,3,5-trimethylcyclohexylideneamino)oxy]methyl ester; n<20> 1.5062; [a]<22> + 6.86° (c = 2.73% in CHCl 3 ). D-2-/p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-[(methylsulfonyl)methyl]ester and benzaldoskim sodium salt, D-2-/p-[(a,a ,α-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-/[(benzylideneamino)oxy]methyl/ester; Fp. 65-66°; fal^ "16, 34° (c = 1.60% in CHCl 3 ). D-2-/p-[(α,α,α-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-[(methylsulfonyl) methyl]ester and ethylmethylketoxime sodium salt, D-2-/p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-/[(sec. butylideneamino)oxy]methyl/ester; Fp. 38 -40°; fQ]p^ +10.34° (c = 2.36% in CHCl 3 ).D-2-/p-[(α,α,α-trifluoro-p-tolyl)oxy]phenoxy/- propionic acid-[(methylsulfonyl)methyl]ester and dipentylketoxime sodium salt; D-2-/p-[(α,α,α-trifluoro-p-tolyl)oxy]-phenoxy/-propionic-20 acid-/[ (1-pentyl-hexylideneamino).oxy]-methyl/ester; nD 1.4913; [a]<22> +11.71° (c = 3.27% in CHCl 3 ). D-2-/p-[ (α,α,α-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-[(methylsulfonylJmethyl]ester and methyl-(2-methyl-1-propenyl)-ketoxime sodium salt, D-2-/p-[(a ,α,α-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-/[(1,3-dimethyl-2-butenylideneamino)oxy] methyl/ester; Mp 52-54°; [a]<22 > -5.75° (c = 0.78% in CHCl3).

Example- 2

A solution of IQ g (0.0307 mol) D-2-/p-[(a,afa-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid in 100 ml of dimethylformamide is added dropwise to a suspension of 1.5 g 55% (0.0307 mol) sodium hydride dispersion in 20 ml of dimethylformamide with stirring. After addition, continue stirring at room temperature until hydrogen evolution is complete. The reaction mixture is stirred for a further 15 minutes and (0.048 mol) N-[(isopropylideneamino)-oxy]-N-methyl-piperidinium iodide and 0.5 g of 15-Crown-5 (polyethylene ether-crown compound with a 15-ring containing 5 oxygen atoms) are added ). After stirring for 2 hours at 110°, the reaction mixture is poured into 500 ml of water and extracted 3 times with 300 ml of ethyl acetate. The entire ethyl acetate solution is then washed twice with 200 ml of water and evaporated, and the residue is recrystallized from diethyl ether/n-hexane. You don't get 2 hours at room temperature. Shake several times with ether, wash ether extracts with sodium dithionite solution and then wash the solution again 8 times with 100 ml of saturated sodium chloride solution and then 5 times with 100 ml of water until neutral reaction. The mixture is treated with activated carbon, filtered and evaporated. The residue is recrystallized from methylene chloride/n-hexane. 2-[p-[(a,a,a-trifluoro-p-tolyl)oxy]-phenoxy/-propionic acid-[(methylsulfonyl)methyl] ester is obtained which melts at 87-88°C.

Analogous to the first paragraph in this example, by using D-2-/p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy/- pro<p>ionic acid, D-2-/p -[(α,α,α-trifluoro-p<->tolyl)oxy]phenoxy/-propionic acid-[(methylthio)methyl]ester; Fp. 47-48°; [a]<22> +31.24°

(c = 1.58% in CHCl 3 ). D-2-[p-(p-chlorophenoxy)phenoxy]-propionic acid D-2-[p-(p-chlorophenoxy)phenoxy]-propionic acid-[(methylthio)-methyl]ester; Fp. 75°; [a]<22> +50.54° (c = 1.34% in CHCl3).

2-[p-(o,p-dichlorophenoxy)phenoxy]-propionic acid 2-[p-(o,p-dichlorophenoxy)phenoxy]-propionic acid-[(methylthio)methyl]ester;

Fp. 54°.

D-2-[p-(p-bromophenoxy)phenoxy]-propionic acid 2-[p-(o,p-dichlorophenoxy)phenoxy]-propionic acid-[(methylthio)-methyl]ester;

Fp. 83-87°; [a]<22> +45.52° (c = 1.81% in CHCl3). D-2-[p-(p-iodophenoxy)phenoxy]-propionic acid D-2-[p-(p-iodophenoxy)phenoxy]-propionic acid-[(methylthio)methyl]-ester; Fp. 71-74°; [a]<22> +41.39° (c = 1.43% in CHCl3). Analogous to the method described in the second section, by using D-2-/p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy/-pro<p>ionic acid-[(methylthio )methyl]ester D-2-/p-[(α,α,α-trifluoro-p-tolyl)oxy]phenoxy/-<p>ropionic acid-[(methylsulfonyl)methyl]ester; Fp. 79-82°; [a]<20> +40.77° (c = 1.66% in CHCl 3 ).

8.0 g of D-2-/p-[(α,α,α-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-/[(isopropylideneamino)oxy]methyl/ester, which melts at 85-86° ; [a]<20> +11.3° (c = 1.2% in CHC13J.

Example 3

I, 75 g of L (-)-lactic acid-/[isopropylideneamino)oxy]-methyl ester, 2.65 g of triphenylphosphine and 2.54 g of p-[(α,α,α-trifluoro-p-tolyl)oxy] -phenol is dissolved at 0° in 10 ml of absolute tetrahydrofuran. 1.75 g of azodicarboxylic acid diethyl ether are added dropwise to the solution while cooling. After the addition, one stirs for a further half an hour, pours the reaction mixture into 100 ml of water, extracts twice with 50 ml of water, dries it over anhydrous sodium sulphate and evaporates. The residue is chromatographed on 20 times the amount of silica gel with n-hexane/ethyl acetate (4:1) and the eluate is evaporated. One recrystallizes from diethyl ether/n-hexane and obtains D-2-/p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid/[isopropylideneamino)-oxy]methyl/ester; Fp. 85°; [a]20 +10.9° (c = 1.33% in CHC13J.

II. Preparation of starting materials:

Example" 4

100 g of 2-/p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy/-pro<p>ionic acid (0.03 mol) and 252 g of sodium bicarbonate (3.0 mol) up -slurry in 2.5 1 dimethyl sulphoxide and then mix slowly with 336.5 ml tert-butyl bromide (3.0 mol). The mixture is stirred overnight at room temperature and the entire mixture and the precipitated thick precipitate are taken up in 5 l of vinegar. The acetic ester solution is washed twice with 1 liter of water, dried over sodium sulphate and evaporated. - The residue is chromatographed on 10 times the amount of silica gel with hexane/acetic ester in the ratio 7:1 and the eluate is evaporated. 2-[p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-[(methylthio)methyl]ester is obtained in the form of an oil-.

40 g of 2-/p-[a,a,a-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-[(methylthio)methyl]ester (0.096 mol) are dissolved in 120 ml of acetone/water in a ratio of 5:1 and mixed slowly with 192 ml of hydrogen peroxide (30% solution). 96 ml of ammonium molybdate solution (35.2 g of ammonium molybdate in 96 ml of water) is added dropwise to the mixture, cooling in an ice bath. Then stir the mix-

2-/p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-[(phenylthio)methyl]ester 2-r/p- [ (a,a ,a-trifluoro- p-tolyloxy]phenoxy/-propionic acid-[(phenylsulfonyl)methyl]ester, mp 89-92°.

D-2-[p-(p-chlorophenoxy ]..phenoxy]-propionic acid-[(methylthio]methyl] ester D-2-[p-(p-chlorophenoxy)phenoxy]-propionic acid-[(methyl-sulfonyUmethyl ] ester ; Mp. 81-83°; [a]<22> +43.42° (c = 1.02% in CHCl 3 ). 2- [p-(o,p-dichlorophenoxy]phenoxy]-propionic acid - [(methylthio).methyl] ester 2-[p-(o,p-dichlorophenoxyl phenoxy]-propionic acid'-[(methylsulfonyl)methyl] ester; Mp. 9.5°. D-2-[p-(p-bromophenoxy )phenoxy]-propionic acid-[(methylthio]methyl] ester D-2-[p-(p<->bromophenoxy)phenoxy]-<p>ro<p>ionic acid-[(methylsulfonyDmethyl] ester; Fp. 84 -87°; [a]<22> +39.20° (c = 1.43% in CHCl3). D-2t[p-(p-iodophenoxy)phenoxy]-propionic acid-[(methylthio)methyl ester D- 2- [p- (p-rhodophenoxy ] phenoxy) -propionic acid- [ (methyla sulfonyDmethyl] ester; Mp. 121-123°; [a]<22> +37.91° (c = 2.66% in CHC13).

Example 5

To a suspension of 10 g (0.11 mol) L ( + )-lactic acid and 94.2 g (1.1 mol) sodium bicarbonate in 200 ml dimethylsulfoxide, 153 ml (1.1 mol) tert is added dropwise. butyl bromide slowly. The reaction mixture is stirred for 48 hours, then poured into 1 liter of water and extracted twice with 100 ml of ethyl acetate. The organic phase is washed 3 times with 200 ml of water and then evaporated. The crude product is chromatographed on 20 times the quantity of silica gel with n-hexane/ethyl acetate (4:1) and the eluate is evaporated. You get! 5.7 g of L(-)-lactic acid [(methylthio)methyl] ester, [α]<20> -39.27° (c = 1.3% in CHCl 3 ).

The above product can also be obtained by heating 11.2 g of L(+)-sodium lactate, 0.5 g of 15-Crown-5 and 9.25 g of chlorodimethylsulphide and a trace of sodium iodide in 100 ml of absolute acetonitrile at reflux temperature. After 6 hours either

IN

the reaction mixture is added to water and processed further as above. 6.1 g of L(-)-lactic acid-[(methylthio)methyl] ester are obtained, ta]20 -38.5° (c = 0.69% in CHCl3).

2.55 g (0.01 mol) p-[(α,α,α-trifluoro-p-tolyl)oxy]-phenol,

1.5 g (0.01 mol) of L(-)-lactic acid-[(methylthio)-methyl]ester and 2.63 g (0.01 mol) of triphenylphosphine are placed in 10 ml of absolute tetrahydrofuran and the whole is cooled to 0° . During cooling, 0.011 mol of azodicarboxylic acid diethyl ester is added dropwise, during which the yellow color of this ester disappears. The reaction mixture is then stirred for 30 minutes at room temperature, poured into 100 ml of water, extracted twice with 50 ml of ethyl acetate and the organic phase is washed neutral with water. The ethyl acetate solution is then evaporated, the residue is chromatographed on 20 times the amount of silica gel with n-hexane/ethyl acetate (9:1) and the eluate is evaporated. After crystallization from diethyl ether/n-hexane, 2.1 g of D-2-/p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-[(methylthio)methyl]ester are obtained ; Fp. 52°j [α]^ +46.87° (c = 0.65% in CHCl 3 ).

Example 6

To 100 ml of 36% formalin at 10° add 100 ml of piperidine

under cooling and then on 73 g of acetone oxime and 75 g of calcium carbonate. The reaction mixture is stirred overnight at room temperature, then taken up in ethyl acetate and the aqueous phase separated. The organic phase is evaporated, taken up in acetone

and mixed with 65 ml of methyl iodide dropwise while cooling, after which the product slowly crystallizes out. After a further 10 hours, the product is filtered off. 291 g of N-[(isopropylideneamino)oxy]-N-methyl-piperidinium iodide are obtained; Fp. 13 2-133°.

Example 7

1.1 g of sodium lactate, 3.5 g of N-[(isopropylideneamino)-oxy]-N-methyl-piperidinium iodide and 0.1 g of 15-Crown-5 in 10 ml of diglycol dimethyl ether are heated for 4 hours at 110° under nitrogen. The reaction mixture is then poured into 50 ml of water and extracted 3 times with ethyl acetate. The organic phase is washed 4 times with water and then evaporated. After chromatograph-

ing the residue on 10 times the amount of silica gel with n-hexane/ethyl acetate (1:1) and evaporating the eluate gives 0.35 g of L(-)-lactic acid-/[(isopropylideneamino)oxy]-methyl/ester; [a]<20> -1.2° (c = 1.50% in CHCl3).

III. Formulation examples:

Example 8

To prepare an emulsifiable concentrate, the following listed ingredients are mixed together:

This mixture is made up to 1 liter with xylene.

Example 9

The active ingredient, for example 2-/p-[(α,α,α-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-/[isopropylideneamino)-oxy]methyl/ ester (compound A in the following table) is dissolved as follows in acetone that a 2% solution of active substance is formed. Shortly before the beginning of the experiment, it is diluted with water to the desired concentration, which in the present experiment is 312 g per hectares.

(When using insoluble active substances, spray powders containing kaolin as an inert diluent are formulated).

The experimental plant is sprayed in a greenhouse with the formulated active substance, and with the help of mercury vapor lamps a 16-hour day is simulated. 3 weeks after spraying, the plants are examined with regard to the effect that has occurred, i.e. % necrosis is determined, as 100% necrosis corresponds to complete destruction of the plant. Solvent effects - if any - are compensated using the "Abbott formula". The results are summarized in the following table.

A = 2-/p-[(α,α,α-trifluoro-p-tolyl)oxy]phenoxy/-propionic acid-/[(isopropylideneamino)oxy]methyl/ester

Example 10

Compound A see example 9

Compound H = D-2-[p-(p-trifluoromethylphenoxy)phenoxy]-propionic acid methyl ester

Example 11

Compound A see example 9

The terms NMP, Tensiofix 7425, Phenylsulfonate CA, Shellsol AB and Nonoxynol used in the above examples 10 and 11 have the following meaning:

NMP: N-methyl-2-pyrrolidone

Tensiofix B 7425': Emulsifier consisting of 60 parts of a block polymer of ethylene oxide and propylene oxide, 20 parts of the calcium salt of a branched dodecylbenzenesulfonic acid and 20 parts of a solvent mixture of isobutanol and C-6-alkylbenzenes.

Phenylsulfonate CA: Mixture of 70 parts of the calcium salt of a branched dodecylbenzenesulfonic acid and 30 parts of a solvent mixture of isobutanol and C1-6-allylbenzenes.

Shellsol AB: Solvent consisting of a mixture of C1Q-alkylbenzenes.

Nonoxynol: Condensation product of nonylphenol and ethylene oxide.

Example 12

The active ingredient is dissolved in acetone in such a way that a 2% solution of the active ingredient is formed. Shortly before the beginning of the experiment, it is diluted with water to the desired concentration, which in the present experiment is 600 g/hectare.

The experimental plants (weeds and useful plants) are sprayed in greenhouses with the formulated active substance, the application dosage being 0.6 kg of active substance/hectare at a spray volume of 1000 l/hectare. Using mercury vapor lamps, a 16-hour day is simulated. 18 days after the treatment, the plants are examined with regard to the effect that has occurred, as 100% necrosis means complete destruction of the weed or the beneficial plant.

The results are summarized in the following table.

Example 13

The active substance is dissolved in acetone in such a way that a 2% solution of active substance is obtained. Shortly before the beginning of the experiment, it is diluted with water containing the wetting agent nonoxynol (condensation product of nonylphenol and ethyleneoxy). The concentration of the wetting agent in the ready-made agent is 0.2% by weight.

The test plants (weeds and useful plants) are sprayed in greenhouses with the formulated active substance, at the application dosage 1.25 kg of active substance per hectare with a spray volume of 1000 l/hectare. Using mercury vapor lamps, a 16-hour day is simulated. 20 days after the treatment, the plants are examined with regard to the effect that has occurred, since 100% necrosis means complete destruction of the weed or the useful plant.

The results are summarized in the following table and the names of the examined compounds A-G and I-Q are listed after the table.

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The examined compounds Compound A = 2- [ p- \\ <x,« /=*--trifluoro-p-tolyl) oxyjf enoxy] -

propionic acid f[(isopropylideneamino)oxyj-j-methyl] ester

Compound B = D-2-fp- [{ <*, <>< ,°«--trif luor-p-tolyl ).oxyJf enoxy} -

propionic acid- f C(isopropylideneamino)oxy]methyl]ester i

in I

! Compound C = D- 2-[ p- f(»< ,«,«*--trifluoro-p-tolyl) oxyjphenoxyj -

propionic acid T C(»^-methyl-benzylideneamino) oxyj-methyl ester

Compound D = D-2-fp-(p-chlorophenoxy)phenoxyj-propionic acid-j

f [(isopropylideneamino ).oxy] methyl ester

Compound E = 2-fp-(o,p-dichlorophenoxy)phenoxy]-propionic acid-f[(isopropylideneamino)oxymethyl ester

Compound F = 2-fp-(o,p-dichlorophenoxy)phenoxy-propionic acid-f £V-methyl-benzylideneamino)oxymethyl ester

Compound G = D-2-[p-(p-bromophenoxy)phenoxy]-propionic acid-f f (isopropylideneamino)oxymethyl ester

Compound I = D-2-fp-(p-iodophenoxy)phenoxy]-propionic acid-TT( isopropylideneamino)oxy]methyl ester

Compound J = D-2-fp- f(«^-,«»^,«<--trifluoro-p-tolyl)oxyjphenoxyj-propionic acid- f (jcyclopentylideneamino)oxyjmethylj ester

Compound K = D-2-fp-f(^,«x-^-trifluoro-p-tolyl)oxyjf enoxy]-propionic acid f pciclohexylideneamino)oxyjmethyl] ester

Compound L = D-2-[ p- f (^,^,<<-trifluoro-p-tolyl)oxy] f enoxy] -

propionic acid f f(cycloheptylideneamino)oxymethyl] ester

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Compound M = D-2- fp- ^<-trifluoro-p-tolyl) oxyjphenoxyj -

propionic acid IC (3,3,5-trimethylcyclohexylidene-amino)oxymethylj ester

! Compound N = D-2-fp- [(*,«*,•<-tr if luor-p-tolyl) oxyjf enoxy] -

propionic acid f£( benzyl idenamino )oxyJmethylJ j ester |

Compound 0 = D-2- [p-f(«*,~,-*-trifluoro-p-tolyl)oxyjf enoxy] -

propionic acid-/"f~(sec. butylideneamino)oxyj I methylj ester ' <

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Compound P = D-2-fp-[(^,-*,-*—trifluoro-p-tolyl)oxy Jf enoxyj-propionic acid- f Ql-pentyl-hexylideneamino oxyj methyl ester

I \

Compound Q = D-2-Tp-Ot-*»"* ,«*-trifluoro-p-tolyl)oxy Jf enoxyj -

propionic acid- TO1 >3-dimethyl-2-butenylideneamino) oxyj methyl] ester j |

Claims (10)

1. Connections, characterized by that they have the general formula where R means hydrogen, alkyl with 1-6 carbon atoms or 2 phenyl, R alkyl with 1-6 carbon atoms, alkenyl with 2-6 carbon atoms, alkynyl with 2-6 carbon atoms or phenyl, or 1 2 R and R together with the carbon atom to which they are attached form , a cycloalkane ring with 4-10 carbon atoms, which may optionally be mono-, di- or tri-substituted with alkyl with 1-3 carbon-3 4 carbon atoms, R is halogen, trifluoromethyl or nitro and R and R^ hydrogen or halogen as racemates and as optical isomers. 2. Compound according to claim 1, characterized in that it is DL-2-Cp-G^^/^-trifluoro-p-tolyl)oxyphenoxypropionic acid-C C(isopropylideneaminoXoxyJ methyl) ester. 3. Compound according to claim 1, characterized in that it is D-2-Cp-£(«r,»£,«><.-trifluoro-p-tolyl)oxy]enoxyj-propionic acid-£ £(isopropylideneamino)oxyjmethyl ester . 4. Compound according to claim 1, characterized in that it is D-2-fp-(p-bromphenoxy)phenoxypropionic acid-CC(isopropylideneamino)oxymethyl]ester. 5-i Compound according to claim 1, characterized in that it is D-2-fp- £{ oc^, oc-trLf fluoro-p-tolyl) oxyj f en-oclyj-propionic acid-f f f(cyclopen tylideneamino) oxyj methylj ester. 6. Compound according to claim 1, characterized in that it contains D-2-fp- (t-trifluoro-p-tolyl)oxyjfenoxyj-propionic acid f f (cyclohexyl idenamino). oxymethylj ester. 7. Compound according to claim 1, characterized in that "it contains D-2-jj?-£( °<, <x., °<.- trifluoro-p-tolyl)oxyjphenoxyJ-propionic acid-fQcycloheptylideneamino)oxyjmethyl] ester. 8. Compound according to claim 1, characterized in that it contains D-2-fp-£(«<:,«<,<x.-trifluoro-p-tolyl)oxyphenoxyj-propionic acid-f f (benzylideneamino)oxyjmethylj ester. 9. Compound according to claim 1, characterized in that it contains D-2-fp-,-^-trifluoro-p-tolyl)oxyphenoxy]-propionic acid-f f(1,3-dimethyl-2-butenylideneamino)oxymethylj ester. 10. Herbicidal agents, characterized in that they contain an effective amount of at least one compound with the general formula where R<1> means hydrogen, alkyl with 1-6 carbon atoms or phenyl, R 2alkyl with 1-6 carbon atoms, alkenyl with 2-6 carbon atoms, alkynyl with 2-6 carbon atoms or phenyl, or R<1>and R 2 form together with the carbon atom to which they are linked to a cycloalkane ring with 4-10 carbon atoms which may optionally be mono-, di- or tri-substituted with alkyl with 1-3 carbon atoms, R<3> is halogen, trifluoromethyl or nitro and R<4 > and R 5 hydrogen or halogen, as racemates and as optical isomers, and an inert carrier material.