CA1142540A - Propionic acid esters - Google Patents
Propionic acid estersInfo
- Publication number
- CA1142540A CA1142540A CA000364790A CA364790A CA1142540A CA 1142540 A CA1142540 A CA 1142540A CA 000364790 A CA000364790 A CA 000364790A CA 364790 A CA364790 A CA 364790A CA 1142540 A CA1142540 A CA 1142540A
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- CA
- Canada
- Prior art keywords
- oxy
- alpha
- methyl
- ester
- propionic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
- C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
- C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
- A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C317/18—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT
The invention is concerned with propionic acid esters of the general formula I
wherein R1 represents a hydrogen atom, an alkyl group containing 1-6 carbon atoms or a phenyl group, R2 represents an alkyl group containing 1-6 carbon atoms, an alkenyl group containing 2-6 carbon atoms, an alkynyl group containing 2-6 carbon atoms or a phenyl group or R1 and R2 together with the carbon atom to which they are attached form a cycloalkane ring containing 4-10 carbon atoms which, if desired, can be mono-, di-or tri-substituted with alkyl containing 1-3 carbon atoms, R3 represents a halogen atom or a trifluoromethyl or nitro group and R4 and R5 each represent a hydrogen or halogen atom, processes for the manufacture thereof, herbicidal compositions which contain at least one of these compounds as the active substance and the use of said compounds or compositions for the control of weeds.
The invention is concerned with propionic acid esters of the general formula I
wherein R1 represents a hydrogen atom, an alkyl group containing 1-6 carbon atoms or a phenyl group, R2 represents an alkyl group containing 1-6 carbon atoms, an alkenyl group containing 2-6 carbon atoms, an alkynyl group containing 2-6 carbon atoms or a phenyl group or R1 and R2 together with the carbon atom to which they are attached form a cycloalkane ring containing 4-10 carbon atoms which, if desired, can be mono-, di-or tri-substituted with alkyl containing 1-3 carbon atoms, R3 represents a halogen atom or a trifluoromethyl or nitro group and R4 and R5 each represent a hydrogen or halogen atom, processes for the manufacture thereof, herbicidal compositions which contain at least one of these compounds as the active substance and the use of said compounds or compositions for the control of weeds.
Description
The present invention is concerned with propionic acid esters. The propionic acid esters provided by the present invention are compounds of the general formula R ~ 0 ~ ~ ~ COOCH20 ~
wherein Rl represents a hydrogen atom, an alkyl group containing 1-6 carbon atoms or a phenyl group, R2 represents an alkyl group containing 1-6 carbon atoms, an alkenyl group containing
wherein Rl represents a hydrogen atom, an alkyl group containing 1-6 carbon atoms or a phenyl group, R2 represents an alkyl group containing 1-6 carbon atoms, an alkenyl group containing
2-6 carbon atoms, an alkynyl group containing 2-6 carbon atoms or a phenyl group or Rl and R2 together with the carbon atom to which they are attached ~orm a cycloalkane ring containing - 15 4-10 carbon atoms which, i, desired, can be mono-, di- or tri-substituted with alkyl containing 1-3 carbon atoms, R3 represents a halogen atom Pa/31.10.80 or a trifluoromethyl or nitro group and R4 and R each represent a hydrogen or halogen atom.
The invention is also concerned with a process for the manufacture of the compounds of formula I, S (pre-emergence and post-emergence) herbicidal compositions which contain at least one compound of formula I as the active substance and the use of said compounds or said herbicidal compositions.
The process provided by the present invention for the manufacture of tne compounds formula I herein-before comprises (a) reacting a salt of an acid of the general formula R3 ~ o ~ O ~ COOH II
wherein R3, R4 and RS have the significance given earlier, with a compound of the general formula RlR2CNOC~2X III
wherein Rl and R2 have the significance given earlier and X represents a leaving group, or (b) reacting a compound of the general formula Z~/coocH2oN~
wherein Z represents a leaving group and and R have the significance given earlier, with a compound of the general formula R~O~OH V
: R4 wherein R3,R4 and RS have the significance given earlier, or with an alkali metal salt thereof, if necessary in the presence of a base, or S (c) reacting a compound of the general formula R ~ O ~ COOCH ~ R6 VI
wherein R6 represents a lower alkyl, an aryl heteroaryl group and R3, R4 and R5 have the significance given earlier, with an oxime of the general formula RlR2cNoH VII
wherein Rl and R2 have the significance given earlier, or with an alkali metal salt thereof in the presence lS of a base.
, O
- s -The alkyl groups containing 1-6 or 1-3 carbon atoms ~lu~e, unless specified otherwise, straight--chain a~ branched-chain hydrocarbon groups containing 1-6 or 1-3 carbon atoms such as methyl, ethyl, propyl, S isopropyl, butyl, isobutyl, tert.butyl and the like.
The term "l~wer alkyl" preferably means an alkyl group containing 1-6 carbon atoms.
The alkenyl and alkynyl groups containing 2-6 carbon atoms include unsaturated straight-chain and branched-chain hydrocarbon groups containing 2-6 carbon atoms such as allyl, butenyl, isobutenyl, pentenyl, isopentenyl and the like as well as propargyl, butynyl, isobutynyl, pentynyl and the like. Especially preferred alkynyl groups are l-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.
The term "aryl" includes, in particular, phenyl, wAich may be substituted with 1-3 lower alkyl groups, as well as naphthyl. The lower alkyl groups can be the same or different.
S Preferred heteroaryl groups are the pyridyl, imidazolyl, thiazolyl and thiophenyl groups.
Preferred compounds of formula I are those in which Rl represents a methyl or ethyl group, those in which R2 represents a methyl, ethyl or phenyl group, those in which R3 represents a chlorine atom or a trifluoromethyl group, those in which R4 represents a hydrogen atom and those in which R5 represents a h ~ ogen atom. The compounds of formula I in which R1 and R2 together with the car~on atom to which they are attached form a cycloalkane ring which may be substituted with alkyl are also preferred.
Especially pre~erred compounds of for~ula I are:
O
2-L p-[(a,a,a,-Trifluoro-p-tolyl)oxy3phenOX~7--propionic acid L [ (isopropylideneamino)oxy]methyl_7 ester and 2-[p-(p-chlorophenoxy)phenoxy}propionic acid S L [ (isopropylideneamino)oxy~methyl_7ester.
Examples of other compounds of formula I are:
2-[p-(2,4-Dichlorophenoxy)phenoxy ]-propionic acid ~ [(isopropylideneamino)oxy~methyl_7ester, 2-[p-(2,4-dichlorophenoxy)phenoxy}-propionic acid L t (-methyl-benzylideneamino)oxy~methyl_7ester, 2-L p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy_7--propionic acid L [ (sec.butylideneamino)oxy]methyl_7 ester, 2-/ p-[(a,a,a-trifluoro-p-tolyl)oxy~phenoxy_7--propionic acid / [(1-pentyl-hexylideneamino)oxy]methyl_7 ester, 2-~ p-~(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid / ~(1,3-dimethyl-2-hutylideneamino)oxy~-methyl 7 ester, ~.
, 2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy~phenoxy 7--propionic acid ~ [(a-methyl-benzylideneamino)oxy]-methyl_7 ester, 2-~ p-~(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid / ~(cyclohexylideneamino~oxy]methyl_7 ester, 2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy_7--propionic acid ~ ~(cyclopentylideneamino)oxy]methyl 7 ester, 2-~ p-~(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid ~ ~(cycloheptylideneamino)oxy]methyl_7 ester, 2-/ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid ~ ~(benzylideneamino)o.xy]methyl_7 ester, 2-~p-(p-bromophenoxy)phenoxy]-propionic acid [(isop~opylideneamino)oxy]methyl 7 ester, 2-~p-(p-nitrophenoxy)phenoxy]-propionic acid ~ E ( isopropylideneamino)oxy]methyl_7 ester and ~ower al~yl-substituted derivatives of the afore-mentioned cyclopentylideneamino, cyclohexylideneamino and cycloheptylideneamino compounds.
O
Especially preferred are the D-isomers of the compounds of formula I and, consequently, the D-isomers of the aforementioned individually named compounds.
In embodiment (a) of the foregoing process for the manufacture of the compounds of 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, for example, the sodium, potassium or lithium salt, an alkaline ear~h metal salt such as, for example, the magnesium, 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 leaving group denoted by X in the compounds of formula III is, for example, a chlorine, bromine or iodine atom, a tosyloxy or mesyloxy group, a hydroxyl group in free or esterified form or one of the following groups:
o ~ N - R8 y ~
wherein R7, R8 and R9, which can be the same or different, each represent an alkyl group, especially an alkyl group containing 1-6 carbon atoms, or two of S - R7, R8 and R9 together also form a C4-C7-alkylene group and Y ~ represents an anion (e.g. a chlorine, bromine, iodine, hydroxyl or sulphate anion);
~S/ y~
R
wherein R10 and Rl , which can be the same or different, each represent an alkyl group, especially an alkyl group containing 1-6 carbon atoms, and Y ~ has the significance given earlier;
ll'~'~S'~O
) Il n 12 wherein R12 represents a lower al~yl, an-aryl or a heteroaryl group and n stands for 1 or 2.
The reaction of a salt of an acid of formula II
with a compound of formula III is preferably carried out in a suitable inert solvent at about -10C to 220C, preferably at room temperature or at an elevated temperature. An especially preferred temperature range lies between 20C and 70C. 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 embodiment (b) of the present process for the manufacture of compounds of formula I, a compound of formula IV is reacted with a compound of formuLa V or with an alkali metal salt thereof ln a manner ~nown per se.
1~25~0 The leaving group denoted by Z in compounds of formula IV is, for example, one of the leaving groups already given above for X, or a hydroxyl group activated by reaction with triphenylphosphine and azodicarboxylic acid or an ester thereof, especially azodicarboxylic acid diethyl ester ~see, e.g. 3ull. Chem.
Soc. Japan 46, 2833 (1973) or Angew. Chem. 88, 111 (1976)].
The reaction according to embodiment (b) is conveniently carried out in an inert organic solvent such as a hydrocarbon (e.g. benzene or toluene), an ether (e.g. diethyl ether, tetrahydrofuran or dimethoxyethane) or hexamethylphosphoric acid triamide.
The temperature and pressure are not critical, the reaction preferably being carried out at a temperature between lS -20C and the reflux temperature of the reaction mixture, preferably between -10C and 30C.
In embodiment (c) of the present process for the manufacture of compounds of formula I, a compound of formula VI is reacted with an oxime of formula VII in the presence of a base (e.g. an alkali metal carbonate3.
ll~Z540 In this embodiment, a cQmpound of fonm~a VI can be diss~lved in an inert organic solvent such as a chlorinated hydrocarbon ~e.g. dichloromethane, chloroform, carbon tetrachloride or trichloroethane), an ether or an ether-liks compound (e.g. tetrahydrofuran, diethyl ether,diisopropyl ether, dimethoxyethane or dioxan), an aromatic hydrocarbon (e.g. benzene, toluene or xylene), dimethylformamide, dimethyl sulphoxide or hexamethyl-phosphoric acid triamide and thereafter the oxime of formula VII (e.g. in the form of an alkali metal salt) is added. The reaction is generally carried out at a temperature between 0C and the boiling point of the reaction mixture, preferably at a temperature between 0C and 50C. The reaction is normally completed after a short time (e.g. a few minutes). The reaction mixture is conveniently poured into water and extracted with an organic solvent (e.g. ethyl acetate). The residue obtained after evaporation is, if necessary, purified by re-crystallisation or chromatography.
Formula I includes not only racemic compounds ~ut also optical isomers, since an asymmetric carbon atom ~o is present in the a-position to the carbonyl group.
The ester moiety can contain further asymmetric carbon atoms. If desired, the racemic compounds can be separated into dextrorotatory and levorotatory compounds according to known processes. Such processes are described, for example, in Industrial and Engineering Chemistry 60 (8) 12-28. The isomers and the racemic mixtures all possess herbicidal activity, but the extent of this activity is different. The D-isomers have the greatest activity, followed by the racemic mixtures and then the L-isomers. In connection with investigations of this type, it has been found that, for example, in certain experimental procedures the D-isomer of 2--/ p-t(a,a,a-trifluoro-p-tolyl)oxy] phenoxy_7-propionic 1~ acid ~ [(isopropylideneamino)oxy]methyl / ester has a greater activity than the racemic mixture.
The isomers can also be manufactured by synthesis from corresponding optically active starting materials.
The D-isomers of the compounds of formula I are, as mentioned earlier, especially preferred and, consequently, the correspondinq starting materials are also especially preferred.
As a result of the nitrogen-car~on double bond in the group of the formula -N ~
~ 2 there are in each case obtained two geometric isomers (when Rl and R2 have different significances), these isomers being called the syn- and anti-forms. In certain cases it is possible to isolate such isomers.
They also form part of the present invention.
The present invention is also concerned with herbicidal compositions which contain as the active ingredient one or more compounds of formula I as defined earlier. These herbicidal compositions conveniently contain at least one of the following inert materials: carrier substances, wetting agents, inert diluents and solvents.
O
The compounds of formula I hereinbefore are especially suitable for controlling weeds, especially slender foxtail (Alopecurus myosuroides) and ~ ~ m~
such as, for example, cock's foot (Echinochloa crus-galli), great foxtail millet (Setaria faberii) and hair-like millet (Panicum capillare) in cereals, especially barley, oats and wheat, as well as in rice, cotton, soya, sugar beet and vegetable plantations. The compounds of formula I are especially suitable for controlling weeds in sugar beet plantations. ~hus, for example, 2--~ p-~(~,a,a-trifluoro-p-tolyl)oxy~phenoxy_7-propionic acid / ~(isopropylideneamino)oxy~methyl_7 ester in a concentration of 1.25 kg/ha possesses sufficient activity against weeds without, however, damaging the sugar beet plantations. In general, a concentration of 0.1-6 kg/ha, preferably 0.6-2.0 kg/ha and especially preferably 1-1.5 kg/ha, is sufficient to produce the desired herbicidal effect with the compounds of formula I.
When R3 represents a trifluoromethyl group, the compounds of formula I can only find limited use in cereal growing, since they are somewhat phytotoxic.
O
These compounds are, however, especially suitable for controlling weeds in rice, cotton, soya, sugar beet and vegetable plantations.
The compounds of formula I are generally insoluble in water and can be formulated according to any of the methods which are usual for insoluble compounds.
When desired, the compounds of formula I can be dissolved in a water-immiscible solvent such as, for example, a high-boiling hydrocarbon, which conveniently contains dissolved emulsifiers, so that it acts as a self-emulsifiable oil upon addition to water.
The compounds of formula I can also be mixed with a wetting agent, in the presence or absence of an inert diluent, to form a we~table powder which is soluble or dispersible in water, or they can be mixed with the inert diluents to form a solid or pulverous product.
Inert diluents with which the compounds of formula I
can be formulated are solid inert media, including pulverous or finely divided solid substances such as, for example, clays, sands, talc, mica, fertilisers and the like, such products being present either in the form 5 ~0 of a dust or as materials having a larger particle size.
~ he wetting agents can be anionic wetting agents such as, for example, soaps, fatty su~phate esters such as dodecyl sodium sulphate, octadecyl sodium S sulphate and cetyl sodium sulphate, fatty-aromatic sulphonates, such as alkylbenzenesulphonates or butyl-naphthalenesulphonates, more complex fatty sulphonates such as the amide condensation products of oleic acid and N-methyltaurine or the sodium sulphonate of dioctyl-succinate.
The wetting agents can also ~e non-ionic wetting agents such as, for example, condensation products of fatty acids, fatty alcohols or ~y substituted phenols with ethylene oxide, fatty acid esters and ethers of sugars or polyvalent alcohols , the products which are obtained from the latter by condensation with ethylene oxide, or the products which are ~nown as block copolymers of ethylene oxide and propylene oxide.
-` 19 -`
The wetting agents can also be cat~onic wetting agents, such as, for example, cetyltrimethylammonium bromide and the like.
The herbicidal compositions provided by the present invention can also be formulated as aerosols, a co-solvent and a wetting agent conveniently being used in addition to the propellant gas, which is suitably a polyhalogenated alkane (e.g~ dichlorodifluoromethane).
~he herbicidal compositions provided by the present invention can contain, in addition to compounds of formula I, synergists and other active ingredients (e.g. insecticides, a¢aricides, bactericides, other herbicides, fungicides, plant growth regulators and fertilisers). Such combination preparations are suitable for increasing the activity or for broadening the spectrum of activity.
The co~ounds of ~oxmula I can be used in different pro-poxtions in their variou$ fieIds o~ ~p~lication~ Thus the present invention provides a method for the control of weeds, which method comprises treating the locus to be protected a~ainst weeds, and/or the weeds, with an effective amount of a compount of formula I as set out above.
The herbicidal compositions provided by the present invention can be formulated in a form which is suitable for storage and transport. Such forms can contain, e.g., 2-90 weight percent of one or more compounds of formula I. These forms can then be diluted with similar or different carrier materials to provide concentrations which are suitable for practical use. In ready-for-use herbi~idal compositions, there can be present active ingredient concentrations of 0.05-80 weight percent. The active ingredient concentration can, however, also be lower or higher.
Depending on the intended use, an active ingredient concentration of 2-8 weight percent or 50-80 weight percent is especially preferred.
The starting materials of formulae II, III, IV, V and VII belon~ to known classes of compounds.
The starting materials of formula VI can be prepared by oxidising a compound of the general formula R~
R ~ O ~ ~ COOCHz_S-R6 VIII
wherein R3, ~4, R5 and R6 have the significance given earlier.
me oxidation can be carried out, for example, using hydrogen peroxide.
The compounds of formulae VI and VIII can be prepared in analogy to the details given in DOS 2 617 804.
Thus-obtained racemates can be resolved in the customary manner.
The compounds of formulae VI and VIII in which R6 represents a heteroaryl group are novel, i.e.
irrespective of whether they are present as racemates 5~0 or in the form of the optical isomers (e.g. the D--isomers). When R6 in the compounds of formulae Vl and VIII represents a lower alkyl group (e.g. a methyl group), an aryl group (e.g. ~phenyl group or a halophenyl group),then the corresponding D-isomers are also novel.
The aforementioned novel compounds of formulae VI
and VIII can be prepared, for example, by reacting the racemate or the D-isomer of a compound of formula II
with a compound of the general formula wherein R6 has the significance given earlier in this paragraph.
This reaction can be carried out in a manner ~nown per se, advantageously in an inert organic solvent such as chloroform or dimethyl sulphoxide and in the presence of dicyclohexylcarbodiimide. ~ thus--obtained compound of formula VIII can then be oxidised, for example with hydrogen peroxide, to give a compound of formula VI.
Especially preferred compounds of formulae VI
and VIII are:
D-2-~p-(p-Bromophenoxy)phenoxy]-propionic acid methylthiomethyl ester, D-2-~p-(p-fluorophenyloxy)phenoxy]-propionic acid methylthiomethyl ester, D-2-~p-(p-nitrophenoxy)phenoxy3-propionic acid methylthiomethyl ester and D-2-~p-(p-trifluoromethylphenoxy)phenoxy~--propionic acid methylthiomethyl ester as well as the corresponding sulphonyl compounds.
The aforementioned compounds of formulae VI and VIII, especially the D-isomers thereof, are also valuable as herbicides, since they exhibit a similar spectrum of activity as the compounds of formula I.
ll ~Z5~0 They can therefore be used for the manufacture of herbicidal compositions in the same manner as described earlier for the compounds of formula I.
The D-isomers have the advantage that, in comparison to the corresponding racemates, they possess, for example, a lower phytotoxicity on cotton and soya beans.
The following Examples illustrate the present invention.
I. Manufacture of the compounds of formula I:
Example 1 36 g of 2-~ p-~(,a,a-trifluoro-p-tolyl)oxy]-phenoxy 7-propionic acid [(methylsulphonyl)methyl]
ester are dissolved in 20 ml of tetrahydrofuran. A
mixture of 0.35 g of acetone oxime sodium salt, dissolved in 20 ml of dimethylformamide, is added to this solution and the mixture is stirred at room temperature for 2 minutes. The mixture is poured into water, extracted with ethyl acetate and washed neutral 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 recrystallised from ether/hexene. The resulting 2-~ p-[(a,a,a--trifluoro-p-tolyl)oxy~ phenoxy_7-propionic acid J ~(isopropylideneamino)oxy~ methyl /ester melts at 76-77C.
In an analogous manner, from D-2-~ p-[(a,a,a-trifluoro-p-tolyljoxy]phenoxy 7--prop~onic acid ~(methylsulphonyl)methyl3 ester and acetone oxime sodium salt there is obtained D-2-~ p--~(a,a,a-trifluoro-p-tolyl)oxy3phenoxy_7-propionic acid ~ ~(isopropylideneamino)oxy]methyl 7 ester; melting point 80-85C; [a]D2 = +11.62(c = 1.25~ in chloroform);
from D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]-phenoxy 7-propionic acid t(methylsulphonyl)methyl3 ester and acetophenone oxime sodium salt there is obtained D-2-~ p-~(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid / [(a-methyl-benzylideneamino)oxy]-methyl_7ester; melting point 63-64C; [a]22= -13.64 (c = 0.75% in chloroform);
from D-2-[p-(p-chlorophenoxy)phenoxy]-propionic acid [(methylsulphonyl)methyl] ester and acetone oxime sodium salt there is obtained D-2-[p-(p-chlorophenoxy)-phenoxy3-propionic acid / ~(isopropylideneamino)oxy3-methyl_7 ester; n20 =1.5480; [a322 =+ 13.58 (c = 1.93% in chloroform);
from 2-[p-(o,p-dichlorophenoxy)phenoxy~-propionic acid [(methylsulphonyl)methyl] ester and acetone oxime sodium salt there is obtained 2-[p-(o,p-dichlorophenoxy)-phenoxy]-propionic acid ~ [(isopropylideneamino)oxy]-methyl_7 ester; nD =1.5557.
from 2-[p-(o,p-dichlorophenoxy)phenoxy]-propionic acid t(methylsulphonyl)methyl~ ester and acetophenone oxime sodium salt there is obtained 2-tp-(o,p--dichlorophenoxy)phenoxy]-propionic acid ~ t(a-methyl--benzylideneamino)oxy]methyl_7 ester; melting point 66-67C;
from D-2-tp-(p-bromophenoxy)phenoxy]-propionic acid t(methylsulphonyl)methyl] ester and acetone oxi~e sodium salt there is obtained D-2-tp-(p-bromophenoxy)-phenoxy]-propionic acid ~ t(isopropylideneamino)oxy]-methyl 7 ester; nD = 1.5598; [a]D2 = +11.92 (c = 1.15~ in chloroform);
ll~Z~i40 from D-2-[p-(p-iodophenoxy)phenoxy]-propionic acid ~(methylsulphonyl)methyl] ester and acetone oxime sodium salt there is obtained D-2-[p-(p-iodophenoxy)-phenoxy]-propionic acid / ~(isopropylideneamino)oxy]_ methyl 7 ester; melting point 40-43C; ~a]D2 =+8.60 ~c = 0.90~ in chloroform);
from D-2-/ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy_7--propionic acid ~(methylsulphonyl)methyl] ester and cyclopentanone oxime sodium salt there is obtained D-2-~ p-[(~,a,a-trifluoro-p-tolyl)oxy]-phenoxy_7--propionic acid ~ ~(cyclopentylideneamino)oxy]methyl_7 ester; melting point 43-45 C; ~a]D = +7.52 (c = 2.28% in chloroform);
from D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid [(methylsulphonyl)methyl_7 ester and cyclohexanone oxime sodium salt there is obtained D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]-phenoxy 7--propionic acid ~ [(cyclohexylideneamino)oxy]methyl 7 ester; melting point 71-73C; [a]D2 = ~5.55 ~c = 1.49% in ch1oroform);
}O
from D-2-/ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy /--propionic acid t(methylsulphonyl)methyl] ester and cycloheptanone oxime sodium salt there is obtained D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy~-phenoxy 7--propionic acid ~ ~(cycloheptylideneamino)oxy] methyl 7 ester; melting point ca 30C; [a~22 = +6.00 (c = 1.96% in chloroform);
from D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid [(methylsulphonyl)methyl] ester and
The invention is also concerned with a process for the manufacture of the compounds of formula I, S (pre-emergence and post-emergence) herbicidal compositions which contain at least one compound of formula I as the active substance and the use of said compounds or said herbicidal compositions.
The process provided by the present invention for the manufacture of tne compounds formula I herein-before comprises (a) reacting a salt of an acid of the general formula R3 ~ o ~ O ~ COOH II
wherein R3, R4 and RS have the significance given earlier, with a compound of the general formula RlR2CNOC~2X III
wherein Rl and R2 have the significance given earlier and X represents a leaving group, or (b) reacting a compound of the general formula Z~/coocH2oN~
wherein Z represents a leaving group and and R have the significance given earlier, with a compound of the general formula R~O~OH V
: R4 wherein R3,R4 and RS have the significance given earlier, or with an alkali metal salt thereof, if necessary in the presence of a base, or S (c) reacting a compound of the general formula R ~ O ~ COOCH ~ R6 VI
wherein R6 represents a lower alkyl, an aryl heteroaryl group and R3, R4 and R5 have the significance given earlier, with an oxime of the general formula RlR2cNoH VII
wherein Rl and R2 have the significance given earlier, or with an alkali metal salt thereof in the presence lS of a base.
, O
- s -The alkyl groups containing 1-6 or 1-3 carbon atoms ~lu~e, unless specified otherwise, straight--chain a~ branched-chain hydrocarbon groups containing 1-6 or 1-3 carbon atoms such as methyl, ethyl, propyl, S isopropyl, butyl, isobutyl, tert.butyl and the like.
The term "l~wer alkyl" preferably means an alkyl group containing 1-6 carbon atoms.
The alkenyl and alkynyl groups containing 2-6 carbon atoms include unsaturated straight-chain and branched-chain hydrocarbon groups containing 2-6 carbon atoms such as allyl, butenyl, isobutenyl, pentenyl, isopentenyl and the like as well as propargyl, butynyl, isobutynyl, pentynyl and the like. Especially preferred alkynyl groups are l-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.
The term "aryl" includes, in particular, phenyl, wAich may be substituted with 1-3 lower alkyl groups, as well as naphthyl. The lower alkyl groups can be the same or different.
S Preferred heteroaryl groups are the pyridyl, imidazolyl, thiazolyl and thiophenyl groups.
Preferred compounds of formula I are those in which Rl represents a methyl or ethyl group, those in which R2 represents a methyl, ethyl or phenyl group, those in which R3 represents a chlorine atom or a trifluoromethyl group, those in which R4 represents a hydrogen atom and those in which R5 represents a h ~ ogen atom. The compounds of formula I in which R1 and R2 together with the car~on atom to which they are attached form a cycloalkane ring which may be substituted with alkyl are also preferred.
Especially pre~erred compounds of for~ula I are:
O
2-L p-[(a,a,a,-Trifluoro-p-tolyl)oxy3phenOX~7--propionic acid L [ (isopropylideneamino)oxy]methyl_7 ester and 2-[p-(p-chlorophenoxy)phenoxy}propionic acid S L [ (isopropylideneamino)oxy~methyl_7ester.
Examples of other compounds of formula I are:
2-[p-(2,4-Dichlorophenoxy)phenoxy ]-propionic acid ~ [(isopropylideneamino)oxy~methyl_7ester, 2-[p-(2,4-dichlorophenoxy)phenoxy}-propionic acid L t (-methyl-benzylideneamino)oxy~methyl_7ester, 2-L p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy_7--propionic acid L [ (sec.butylideneamino)oxy]methyl_7 ester, 2-/ p-[(a,a,a-trifluoro-p-tolyl)oxy~phenoxy_7--propionic acid / [(1-pentyl-hexylideneamino)oxy]methyl_7 ester, 2-~ p-~(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid / ~(1,3-dimethyl-2-hutylideneamino)oxy~-methyl 7 ester, ~.
, 2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy~phenoxy 7--propionic acid ~ [(a-methyl-benzylideneamino)oxy]-methyl_7 ester, 2-~ p-~(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid / ~(cyclohexylideneamino~oxy]methyl_7 ester, 2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy_7--propionic acid ~ ~(cyclopentylideneamino)oxy]methyl 7 ester, 2-~ p-~(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid ~ ~(cycloheptylideneamino)oxy]methyl_7 ester, 2-/ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid ~ ~(benzylideneamino)o.xy]methyl_7 ester, 2-~p-(p-bromophenoxy)phenoxy]-propionic acid [(isop~opylideneamino)oxy]methyl 7 ester, 2-~p-(p-nitrophenoxy)phenoxy]-propionic acid ~ E ( isopropylideneamino)oxy]methyl_7 ester and ~ower al~yl-substituted derivatives of the afore-mentioned cyclopentylideneamino, cyclohexylideneamino and cycloheptylideneamino compounds.
O
Especially preferred are the D-isomers of the compounds of formula I and, consequently, the D-isomers of the aforementioned individually named compounds.
In embodiment (a) of the foregoing process for the manufacture of the compounds of 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, for example, the sodium, potassium or lithium salt, an alkaline ear~h metal salt such as, for example, the magnesium, 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 leaving group denoted by X in the compounds of formula III is, for example, a chlorine, bromine or iodine atom, a tosyloxy or mesyloxy group, a hydroxyl group in free or esterified form or one of the following groups:
o ~ N - R8 y ~
wherein R7, R8 and R9, which can be the same or different, each represent an alkyl group, especially an alkyl group containing 1-6 carbon atoms, or two of S - R7, R8 and R9 together also form a C4-C7-alkylene group and Y ~ represents an anion (e.g. a chlorine, bromine, iodine, hydroxyl or sulphate anion);
~S/ y~
R
wherein R10 and Rl , which can be the same or different, each represent an alkyl group, especially an alkyl group containing 1-6 carbon atoms, and Y ~ has the significance given earlier;
ll'~'~S'~O
) Il n 12 wherein R12 represents a lower al~yl, an-aryl or a heteroaryl group and n stands for 1 or 2.
The reaction of a salt of an acid of formula II
with a compound of formula III is preferably carried out in a suitable inert solvent at about -10C to 220C, preferably at room temperature or at an elevated temperature. An especially preferred temperature range lies between 20C and 70C. 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 embodiment (b) of the present process for the manufacture of compounds of formula I, a compound of formula IV is reacted with a compound of formuLa V or with an alkali metal salt thereof ln a manner ~nown per se.
1~25~0 The leaving group denoted by Z in compounds of formula IV is, for example, one of the leaving groups already given above for X, or a hydroxyl group activated by reaction with triphenylphosphine and azodicarboxylic acid or an ester thereof, especially azodicarboxylic acid diethyl ester ~see, e.g. 3ull. Chem.
Soc. Japan 46, 2833 (1973) or Angew. Chem. 88, 111 (1976)].
The reaction according to embodiment (b) is conveniently carried out in an inert organic solvent such as a hydrocarbon (e.g. benzene or toluene), an ether (e.g. diethyl ether, tetrahydrofuran or dimethoxyethane) or hexamethylphosphoric acid triamide.
The temperature and pressure are not critical, the reaction preferably being carried out at a temperature between lS -20C and the reflux temperature of the reaction mixture, preferably between -10C and 30C.
In embodiment (c) of the present process for the manufacture of compounds of formula I, a compound of formula VI is reacted with an oxime of formula VII in the presence of a base (e.g. an alkali metal carbonate3.
ll~Z540 In this embodiment, a cQmpound of fonm~a VI can be diss~lved in an inert organic solvent such as a chlorinated hydrocarbon ~e.g. dichloromethane, chloroform, carbon tetrachloride or trichloroethane), an ether or an ether-liks compound (e.g. tetrahydrofuran, diethyl ether,diisopropyl ether, dimethoxyethane or dioxan), an aromatic hydrocarbon (e.g. benzene, toluene or xylene), dimethylformamide, dimethyl sulphoxide or hexamethyl-phosphoric acid triamide and thereafter the oxime of formula VII (e.g. in the form of an alkali metal salt) is added. The reaction is generally carried out at a temperature between 0C and the boiling point of the reaction mixture, preferably at a temperature between 0C and 50C. The reaction is normally completed after a short time (e.g. a few minutes). The reaction mixture is conveniently poured into water and extracted with an organic solvent (e.g. ethyl acetate). The residue obtained after evaporation is, if necessary, purified by re-crystallisation or chromatography.
Formula I includes not only racemic compounds ~ut also optical isomers, since an asymmetric carbon atom ~o is present in the a-position to the carbonyl group.
The ester moiety can contain further asymmetric carbon atoms. If desired, the racemic compounds can be separated into dextrorotatory and levorotatory compounds according to known processes. Such processes are described, for example, in Industrial and Engineering Chemistry 60 (8) 12-28. The isomers and the racemic mixtures all possess herbicidal activity, but the extent of this activity is different. The D-isomers have the greatest activity, followed by the racemic mixtures and then the L-isomers. In connection with investigations of this type, it has been found that, for example, in certain experimental procedures the D-isomer of 2--/ p-t(a,a,a-trifluoro-p-tolyl)oxy] phenoxy_7-propionic 1~ acid ~ [(isopropylideneamino)oxy]methyl / ester has a greater activity than the racemic mixture.
The isomers can also be manufactured by synthesis from corresponding optically active starting materials.
The D-isomers of the compounds of formula I are, as mentioned earlier, especially preferred and, consequently, the correspondinq starting materials are also especially preferred.
As a result of the nitrogen-car~on double bond in the group of the formula -N ~
~ 2 there are in each case obtained two geometric isomers (when Rl and R2 have different significances), these isomers being called the syn- and anti-forms. In certain cases it is possible to isolate such isomers.
They also form part of the present invention.
The present invention is also concerned with herbicidal compositions which contain as the active ingredient one or more compounds of formula I as defined earlier. These herbicidal compositions conveniently contain at least one of the following inert materials: carrier substances, wetting agents, inert diluents and solvents.
O
The compounds of formula I hereinbefore are especially suitable for controlling weeds, especially slender foxtail (Alopecurus myosuroides) and ~ ~ m~
such as, for example, cock's foot (Echinochloa crus-galli), great foxtail millet (Setaria faberii) and hair-like millet (Panicum capillare) in cereals, especially barley, oats and wheat, as well as in rice, cotton, soya, sugar beet and vegetable plantations. The compounds of formula I are especially suitable for controlling weeds in sugar beet plantations. ~hus, for example, 2--~ p-~(~,a,a-trifluoro-p-tolyl)oxy~phenoxy_7-propionic acid / ~(isopropylideneamino)oxy~methyl_7 ester in a concentration of 1.25 kg/ha possesses sufficient activity against weeds without, however, damaging the sugar beet plantations. In general, a concentration of 0.1-6 kg/ha, preferably 0.6-2.0 kg/ha and especially preferably 1-1.5 kg/ha, is sufficient to produce the desired herbicidal effect with the compounds of formula I.
When R3 represents a trifluoromethyl group, the compounds of formula I can only find limited use in cereal growing, since they are somewhat phytotoxic.
O
These compounds are, however, especially suitable for controlling weeds in rice, cotton, soya, sugar beet and vegetable plantations.
The compounds of formula I are generally insoluble in water and can be formulated according to any of the methods which are usual for insoluble compounds.
When desired, the compounds of formula I can be dissolved in a water-immiscible solvent such as, for example, a high-boiling hydrocarbon, which conveniently contains dissolved emulsifiers, so that it acts as a self-emulsifiable oil upon addition to water.
The compounds of formula I can also be mixed with a wetting agent, in the presence or absence of an inert diluent, to form a we~table powder which is soluble or dispersible in water, or they can be mixed with the inert diluents to form a solid or pulverous product.
Inert diluents with which the compounds of formula I
can be formulated are solid inert media, including pulverous or finely divided solid substances such as, for example, clays, sands, talc, mica, fertilisers and the like, such products being present either in the form 5 ~0 of a dust or as materials having a larger particle size.
~ he wetting agents can be anionic wetting agents such as, for example, soaps, fatty su~phate esters such as dodecyl sodium sulphate, octadecyl sodium S sulphate and cetyl sodium sulphate, fatty-aromatic sulphonates, such as alkylbenzenesulphonates or butyl-naphthalenesulphonates, more complex fatty sulphonates such as the amide condensation products of oleic acid and N-methyltaurine or the sodium sulphonate of dioctyl-succinate.
The wetting agents can also ~e non-ionic wetting agents such as, for example, condensation products of fatty acids, fatty alcohols or ~y substituted phenols with ethylene oxide, fatty acid esters and ethers of sugars or polyvalent alcohols , the products which are obtained from the latter by condensation with ethylene oxide, or the products which are ~nown as block copolymers of ethylene oxide and propylene oxide.
-` 19 -`
The wetting agents can also be cat~onic wetting agents, such as, for example, cetyltrimethylammonium bromide and the like.
The herbicidal compositions provided by the present invention can also be formulated as aerosols, a co-solvent and a wetting agent conveniently being used in addition to the propellant gas, which is suitably a polyhalogenated alkane (e.g~ dichlorodifluoromethane).
~he herbicidal compositions provided by the present invention can contain, in addition to compounds of formula I, synergists and other active ingredients (e.g. insecticides, a¢aricides, bactericides, other herbicides, fungicides, plant growth regulators and fertilisers). Such combination preparations are suitable for increasing the activity or for broadening the spectrum of activity.
The co~ounds of ~oxmula I can be used in different pro-poxtions in their variou$ fieIds o~ ~p~lication~ Thus the present invention provides a method for the control of weeds, which method comprises treating the locus to be protected a~ainst weeds, and/or the weeds, with an effective amount of a compount of formula I as set out above.
The herbicidal compositions provided by the present invention can be formulated in a form which is suitable for storage and transport. Such forms can contain, e.g., 2-90 weight percent of one or more compounds of formula I. These forms can then be diluted with similar or different carrier materials to provide concentrations which are suitable for practical use. In ready-for-use herbi~idal compositions, there can be present active ingredient concentrations of 0.05-80 weight percent. The active ingredient concentration can, however, also be lower or higher.
Depending on the intended use, an active ingredient concentration of 2-8 weight percent or 50-80 weight percent is especially preferred.
The starting materials of formulae II, III, IV, V and VII belon~ to known classes of compounds.
The starting materials of formula VI can be prepared by oxidising a compound of the general formula R~
R ~ O ~ ~ COOCHz_S-R6 VIII
wherein R3, ~4, R5 and R6 have the significance given earlier.
me oxidation can be carried out, for example, using hydrogen peroxide.
The compounds of formulae VI and VIII can be prepared in analogy to the details given in DOS 2 617 804.
Thus-obtained racemates can be resolved in the customary manner.
The compounds of formulae VI and VIII in which R6 represents a heteroaryl group are novel, i.e.
irrespective of whether they are present as racemates 5~0 or in the form of the optical isomers (e.g. the D--isomers). When R6 in the compounds of formulae Vl and VIII represents a lower alkyl group (e.g. a methyl group), an aryl group (e.g. ~phenyl group or a halophenyl group),then the corresponding D-isomers are also novel.
The aforementioned novel compounds of formulae VI
and VIII can be prepared, for example, by reacting the racemate or the D-isomer of a compound of formula II
with a compound of the general formula wherein R6 has the significance given earlier in this paragraph.
This reaction can be carried out in a manner ~nown per se, advantageously in an inert organic solvent such as chloroform or dimethyl sulphoxide and in the presence of dicyclohexylcarbodiimide. ~ thus--obtained compound of formula VIII can then be oxidised, for example with hydrogen peroxide, to give a compound of formula VI.
Especially preferred compounds of formulae VI
and VIII are:
D-2-~p-(p-Bromophenoxy)phenoxy]-propionic acid methylthiomethyl ester, D-2-~p-(p-fluorophenyloxy)phenoxy]-propionic acid methylthiomethyl ester, D-2-~p-(p-nitrophenoxy)phenoxy3-propionic acid methylthiomethyl ester and D-2-~p-(p-trifluoromethylphenoxy)phenoxy~--propionic acid methylthiomethyl ester as well as the corresponding sulphonyl compounds.
The aforementioned compounds of formulae VI and VIII, especially the D-isomers thereof, are also valuable as herbicides, since they exhibit a similar spectrum of activity as the compounds of formula I.
ll ~Z5~0 They can therefore be used for the manufacture of herbicidal compositions in the same manner as described earlier for the compounds of formula I.
The D-isomers have the advantage that, in comparison to the corresponding racemates, they possess, for example, a lower phytotoxicity on cotton and soya beans.
The following Examples illustrate the present invention.
I. Manufacture of the compounds of formula I:
Example 1 36 g of 2-~ p-~(,a,a-trifluoro-p-tolyl)oxy]-phenoxy 7-propionic acid [(methylsulphonyl)methyl]
ester are dissolved in 20 ml of tetrahydrofuran. A
mixture of 0.35 g of acetone oxime sodium salt, dissolved in 20 ml of dimethylformamide, is added to this solution and the mixture is stirred at room temperature for 2 minutes. The mixture is poured into water, extracted with ethyl acetate and washed neutral 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 recrystallised from ether/hexene. The resulting 2-~ p-[(a,a,a--trifluoro-p-tolyl)oxy~ phenoxy_7-propionic acid J ~(isopropylideneamino)oxy~ methyl /ester melts at 76-77C.
In an analogous manner, from D-2-~ p-[(a,a,a-trifluoro-p-tolyljoxy]phenoxy 7--prop~onic acid ~(methylsulphonyl)methyl3 ester and acetone oxime sodium salt there is obtained D-2-~ p--~(a,a,a-trifluoro-p-tolyl)oxy3phenoxy_7-propionic acid ~ ~(isopropylideneamino)oxy]methyl 7 ester; melting point 80-85C; [a]D2 = +11.62(c = 1.25~ in chloroform);
from D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]-phenoxy 7-propionic acid t(methylsulphonyl)methyl3 ester and acetophenone oxime sodium salt there is obtained D-2-~ p-~(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid / [(a-methyl-benzylideneamino)oxy]-methyl_7ester; melting point 63-64C; [a]22= -13.64 (c = 0.75% in chloroform);
from D-2-[p-(p-chlorophenoxy)phenoxy]-propionic acid [(methylsulphonyl)methyl] ester and acetone oxime sodium salt there is obtained D-2-[p-(p-chlorophenoxy)-phenoxy3-propionic acid / ~(isopropylideneamino)oxy3-methyl_7 ester; n20 =1.5480; [a322 =+ 13.58 (c = 1.93% in chloroform);
from 2-[p-(o,p-dichlorophenoxy)phenoxy~-propionic acid [(methylsulphonyl)methyl] ester and acetone oxime sodium salt there is obtained 2-[p-(o,p-dichlorophenoxy)-phenoxy]-propionic acid ~ [(isopropylideneamino)oxy]-methyl_7 ester; nD =1.5557.
from 2-[p-(o,p-dichlorophenoxy)phenoxy]-propionic acid t(methylsulphonyl)methyl~ ester and acetophenone oxime sodium salt there is obtained 2-tp-(o,p--dichlorophenoxy)phenoxy]-propionic acid ~ t(a-methyl--benzylideneamino)oxy]methyl_7 ester; melting point 66-67C;
from D-2-tp-(p-bromophenoxy)phenoxy]-propionic acid t(methylsulphonyl)methyl] ester and acetone oxi~e sodium salt there is obtained D-2-tp-(p-bromophenoxy)-phenoxy]-propionic acid ~ t(isopropylideneamino)oxy]-methyl 7 ester; nD = 1.5598; [a]D2 = +11.92 (c = 1.15~ in chloroform);
ll~Z~i40 from D-2-[p-(p-iodophenoxy)phenoxy]-propionic acid ~(methylsulphonyl)methyl] ester and acetone oxime sodium salt there is obtained D-2-[p-(p-iodophenoxy)-phenoxy]-propionic acid / ~(isopropylideneamino)oxy]_ methyl 7 ester; melting point 40-43C; ~a]D2 =+8.60 ~c = 0.90~ in chloroform);
from D-2-/ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy_7--propionic acid ~(methylsulphonyl)methyl] ester and cyclopentanone oxime sodium salt there is obtained D-2-~ p-[(~,a,a-trifluoro-p-tolyl)oxy]-phenoxy_7--propionic acid ~ ~(cyclopentylideneamino)oxy]methyl_7 ester; melting point 43-45 C; ~a]D = +7.52 (c = 2.28% in chloroform);
from D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid [(methylsulphonyl)methyl_7 ester and cyclohexanone oxime sodium salt there is obtained D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]-phenoxy 7--propionic acid ~ [(cyclohexylideneamino)oxy]methyl 7 ester; melting point 71-73C; [a]D2 = ~5.55 ~c = 1.49% in ch1oroform);
}O
from D-2-/ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy /--propionic acid t(methylsulphonyl)methyl] ester and cycloheptanone oxime sodium salt there is obtained D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy~-phenoxy 7--propionic acid ~ ~(cycloheptylideneamino)oxy] methyl 7 ester; melting point ca 30C; [a~22 = +6.00 (c = 1.96% in chloroform);
from D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid [(methylsulphonyl)methyl] ester and
3,3,5-trimethylcyclohexanone oxime sodium salt there is obtained D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]-phenoxy 7-propionic acid ~ [(3,3,5-trimethylcyclo-hexylideneamino)oxy]methyl 7 ester; n20 = 1.5062;
[a]D = +6.86 (c = 2.73% in chloroform);
lS from D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy /--propionic acid ~(methylsulphonyl)methyl} ester and benzaldoxime sodium salt there is obtained ~-2-~ p--[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7-propionic acid ~ [(benzylideneamino)oxy]methyl 7 ester; melting point 65-66C; [alD = -16.34 (c = 1.60~ in chloroform);
from D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy_7--propionic acid [(methylsulphonyl)methyl] ester and ethyl methyl ketoxime sodium salt there is obtained D-2-l p-~(a,a,a-trifluoro-p-tolyl)oxy]phenoxy_7--propionic acid ~ t(sec.butylideneamino)oxy]methyl_7 ester; melting point 38-40C; [a}D2 = + 10.34 (c = 2.36% in chloroform);
from D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy_/--propionic acid ~(methylsulphonyl)methyl] ester and dipentyl ketoxime ~x~ t ~ ~ d~Ed ~2-~(a,a,~
-trifluoro-p-tolyl)oxy]-phenoxy 7-propionic acid ~ ~(l-pentyl-hexylideneamino)oxy] methyl 7 ester;
nD = 1.4913; ~a]D2 = ~11.71 (c = 3.27% in chloroform);
from D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid [(methylsulphonyl)methyl] ester and methyl (2-methyl-1-propenyl) ketoxime sodium salt there is obtained D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]-phenoxy_7-propionic acid ~ [~1,3-dimethyl-2-buten-ylideneamino)oxy]methyl 7 ester; melting point 52 -54 C; [a~D = -5.7S (c = 0.78% in chloroform~.
}0 Example 2 A solution of 10 g (0.0307 mol) of D-2-/ p-t(Q,a,a--trifluoro-p-tolyl)oxy]phenoxy 7-propionic acid in 100 ml of dimethylformamide is added dropwise while stirring S to a suspension of l.S g of 55% sodium hydride dispersion (0.0307 mol) in 20 ml of dimethylformamide. After completion of the addition, the mixture is stirred at room temperature until the hydrogen evolution has stopped. The mixture is stirred for a further lS minutes and there are added thereto 15 g (0.048 mol) of N-[(iso-propylideneamino)oxy]-N-methyl-piperidinium iodide and 0.5 g of lS-crown-5 (the polyethylene ether-crown compound with a 15-ring containing ~ oxygen atoms). After stirring at 110C for 2 hours, the mixture is poured into 500 ml of water and extracted three times w~th 300 ml of ethyl acetate each time. The ethyl acetate extracts are combined, washed twice with 200 ml of water each time and then evaporated, the residue being subsequently recrysta}lised from diethyl etherJn-hexane. There are o~tained 8,o g of D-2-/ p-~(a,a,a-trifluoro-p-tolyl)oxy~-phenoxy_~-propionic acid / ~(isopropylideneamino)oxyl-}V
methyl_/ ester which melts at 85-86C; [a]20 = +11~3 (c = 1.2% in chloroform).
Example 3 1.75 g of L ~-)-lactic acid ~ ~(isopropylideneamino)-oxy~methyl / ester, 2.65 g of triphenylphosphine and 2.54 g of p-[(a,a,a-trifluoro-p-tolyl)oxy~-phenol are dissolved at 0C in 10 ml of absolute tetrahydrofuran.
1.75 g of azodicarboxylic acid diethyl ether are added dropwise to the solution while cooling. After completion of the addition, the mixture is stirred for 0.5 hour, then poured into 100 ml of water, extracted twice with 50 ml of water each time, dried over anhydrous sodiium sulphate and evaporated. The residue is chromatographed on a 20-fold amount of silica gel with n-hexane/ethyl acetate (4:1) and the eluate is evaporated. The residue is crystallised from diethyl ether/n-hexane and there is obtained D-2-/ p-~( a, a, a- trif}uoro-p-tolyl)oxy~phenoxy ? ~
-propionic acid / [(isopropylideneamino)oxy~methyl_/
ester; melting point 85~C; ~a~D = flO.9 ~c = 1.33%
in chloroform).
II. Preparation of the startinq materials:
ExamPle 4 100 g(0.03 mol) of 2-~ p-~(a,a,-trifluoro-p--tolyl)oxy]-phenoxy 7-propionic acid and 252 g (3.0 mol) of sodium bicarbonate are suspended in 2.5 litres of dimethyl sulphoxide and thereafter treated slowly with 336.5 ml (3.0 mol) of tert.butyl bromide. The mixture is stirred at room temperature overnight. The mixture, including the separated thick precipitate, is subsequently taken up in 5 litres of ethyl acetate. The ethyl acetate solution is washed twice with 1 litre of water, dried over sodium sulphate and evaporated. The residue is chromatographed on a 10-fold amount of silica gel with hexane/ethyl acetate (7:1) and the eluate is evaporated. There is obtained 2-l p-[(a,a,a-trifluoro--p-tolyl)oxyl phenoxy /-propionic acid [(methylthio)-methyl3 ester in the form of an oil.
40 g (0.096 mol) of 2-~ p-[( a,a,a-trifluoro-p--tolyl)oxy] phenoxy 7-propionic acid ~ (methylthio)-methyl3 ester are dissolved in 120 ml of acetone/water (5:1) and treated slowly with 192 ml of a 30% solution of hydrogen peroxide. 96 ml of ammonium molybdate solution (35.2 g of ammonium molybdate in 96 ml of water) are added dropwise to the mixture which is cooled with an ice-bath. The mixture is stirred at room temperature for 2 hours. It is .then extracted several times with ether, the ether extract is washed with sodium dithionite solution and the solution is again washed neutral with eight 100 ml portions of saturated sodlum chloride solution and subsequently with five 100 ml portions of water. The mixture is treated with active carbon, filtered and e~aporated.
The residue is recrystallised from methylene chloride/
n-hexane. There is obtained 2-/ p-[(,a,a-trifluoro--p-tolyl)oxy~phenoxy_7-propionic acid ~(methylsulphonyl)-methyl] ester which melts at 87-88C.
In a manner analogous to that described in the first paragraph of thls Example, from D-2-~ p-t(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid there is obtained D-2-~ p-[(a,a,a--trifluoro-p-tolyl)oxy~phenoxy 7-propionic acid ~(methylthio)methyl] ester; melting point 47-48C;
~a]D2= +31.24 (c = 1.58% in chloroform);
from D-2-[p-(p-chlorophenoxy)phenoxy]-propionic acid there is obtained D-2-[p-(p-chlorophen~xy)-phenoxy]-propionic acid [(methylthio) methy~] ester;
melting point 75C; [a]D2= + 50.54 (c = 1.34% in chloroform);
from 2-~p-(o,p-dichlorophenoxy)phenoxy~-propionic acid there is obtained 2-~p-(o,p-dichlorophenoxy)-phenoxy]-propionic acid [(methylthio)methyl] ester;
melting point 54C;
from D-2-[p-(p-bromophenoxy)phenoxyl-propionic acid there is obtained 2-[p-(o,p-dichlorophenoxy)-phenoxyl-propionic acid [(methylthio)methyl] ester;
melting point 83-87C; [~322 = +45.52 (c = 1.81%
in chloroform);
from D-2-[p-(p-iodophenoxy3phenoxy~-propionic acid there is obtained D-2-[p-(p-iodophenoxy)phenoxy~--propionic acid ~(methylthio)methyl~ ester; melting point 71-74C; [a]22 = +41.39 (c = 1.43% in chloroform);
In a manner analogous to that described in the second paragraph of this Example, from D-2-L p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy_7--propionic acid [(methylthio)methyl] ester there is obtained D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid ~(methylsulphonyl)methyl] ester;
melting point 79-82C; ~3DO = +40 77 (c = 1.66%
in chloroform);
from 2-~ p-~(a,a,a-trifluoro-p-tolyl)oxy]phenoxy_7--propionic acid [(phenylthio)methyl ester there is obtained 2-l p-~(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid ~(phenylsulphonyl)methyll ester;
melting point 89-92C;
from D-2-[p-(p-chlorophenoxy)phenoxy]-propionic acid [(methylthio)methyl] ester there is obtained D-2-[p-(p-chlorophenoxy)phenoxy]-propionic acid [(methylsulphonyl)methyl] ester; melting point 81-83C; ~a]D2= +43.42 (c = 1.02% in chloroform);
from 2-[p-(o,p-dichlorophenoxy)phenoxy]-propionic acid [(methylthio)methyl] ester there is obtained 2-[p-(o,p-dichlorophenoxy)phenoxy3-propionic acid [(methylsulphonyl)methyll ester; melting point 95C;
from D-2-tp-(p-bromophenoxy)phenoxy]-propionic acid r (methylthio)methyl~ ester there is o~tained D-2-[p-(p-bromophenoxy)phenoxy]-propionic acid [(methylsulphonyl)methyl] ester; melting point 84-87C; [a]D2= +39.20 (c = 1.43~ in chloroform);
from D-2-[p-(p-iodophenoxy)phenoxy3-propionic acid - [(methylthio)methyl] ester there is obtained D-2-[p--(p-iodophenoxy)phenoxy]-propionic acid ~(methylsulphonyl)-methyl] ester; melting point 121~-123~C; ~a3D2= +37,9t (c = 2.66~ in chloroform).
l~z~
Example 5 153 ml (1.1 mol) of tert.butyl bromide are slowly added dropwise to a suspension of 10 g (0.11 mol) of L (+)-lactic acid and 94.2 g (1.1 mol) of sodium bicarbonate in 200 ml of dimethyl sulphoxide. The mixture is stirred for 48 hours, then poured into 1 litre of water and extracted twice with 100 ml of ethyl acetate each time. The organic phase is back-washed three times with 200 ml of water each time and subsequently evaporated. The crude product is chromatographed on a 20-fold amount of silica gel with n-hexane/ethyl acetate (4:1) and the eluate is evaporated. There are obtained 5.7 g of L (-)-lactic acid ~(methylthio)methyl] ester;
[a]20 = -39.27 (c = 1.3~ in chloroform).
The foregoing ester can also be obtained by heating 11.2 g of L (+)-sodium lactate, 0.5 g of 1 ~crown-5, 9.25 g of chlorodimethyl sulphide and a trace of sodium iodide in 100 ml of absolute acetonitrile at the reflux temperature of the mixture. After 6 hours, the mixture is poured into water and worked-up in the manner 5'~0 described in the preceding paragraph. There are obtained 6.1 g of L (-)-lactic acid ~(methylthio)-methyl] ester; ~a]20 = _ 3 8.5 (c = 0.69% in chloroform).
2.55 g (0.01 mol) of p-~(~,a,a-trifluoro-p-tolyl)-ox~lphenol, 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 mixture is cooled to 0C. While cooling there is added dropwise 0.011 mol of azodicar~oxylic acid diethyl ester, the yellow colour of this ester disappearing during the addition. The mixture is then stirred at room temperature for 30 minutes, poured into 100 ml of water, extracted twice with 50 ml of ethyl acetate each time and the organic lS phase is washed neutral with water. The ethyl acetate solution is then evaporated, the residue is chromatographed on a 20-fold amount of silica gel with n-hexane/ethyl acetate (9:1) and the eluate is evaporated. After crystallisation from diethyl ether/n-hexane, there are obtained 2.1 g of D-2-/ p-~(a,~ trifluoro-p-tolyl)oxyl-phenoxy 7-propionic acid ~(methylthio)methyll ester;
meltins point 52C; ~a~20 = +46.87~ (c = 0.65% in chloroform).
Example 6 To 100 ml of 36% formalin at 10C are added dropwise while cooling 100 ml of piperidine and t~ereupon 73 g of acetone oxime as well as 75 g of potassium carbonate. The mixture is stirred at room temperature overnight, then taken up in ethyl acetate and the aqueous phase is separated. The organic phase is evaporated, the residue is taken up in acetone and treated dropwise while cooling with 6S ml of methyl iodide, whereafter the product slowly crystallises out.
After a further 10 hours, the product is filtered off.
There are obtained 291 g of N-[(isopropylideneamino)oxy]--N-methyl-piperidinium iodide; melting point 132-133C.
Example 7 1.1 g of sodium lactate, 3.5 g of N-[(isopropylidene-amino)oxy~-N-methyl-piperidinium iodide and 0.1 g of 1 ~
-crown-5 in 10 ml of diglycol dimethyl ether are heated at 110C under nitrogen for 4 hours. The mixture is then poured into 50 ml of water and extracted three times with ethyl acetate. The organic phase is washed four times with water and subsequently evaporated. After chromatography of the residue on a 10-fold amount of silica gel with n-hexane/ethyl acetate (1:1) and evaporation of the elua~e, there is obtained 0.35 g of L (-)-lactic acid ~ ~(isopropylideneamino)oxy3methyl_7 ester; [a]20 = -1.2 (c = 1.50% in chloroform).
I}I. Formulation Examples-ExamPle 8 - An emulsifiable concentrate is produced by mixing the following ingredients with one another:
Compound of formula I S00 g Condensation product of an alkylphenol and ethylene oxide; calcium dodecyl-benzenesulphonic acid 100 g Epoxidated soya oil with an oxirane oxygen content of about 6% 25 g Butylated hydroxytoluene 10 g This mixture is made up to l litre with xylene.
Example 9 The active ingredient of formula I, for example 2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy~phenoxy_7-propionic acid ~ ~tisopropylideneamino)oxy]methyl 7 ester (compound A ~n the following Table ) is dissolved in acetone to give a 2% solution of active ingredient.
Shortly before the beginning of the experiment the solution is diluted with water to provide the desired concentration, which in the present experiment is 312 g/ha.
(When an insoluble active ingredient is used, spray powders which contain kaolin as the inert diluent are formulated.1 The test plants are sprayed in a greenhouse with the formulated active ingredient, a 16 hours day being simulated by means of mercury vapour lamps. 3 weeks after the spraying the plants are examined for the effects which have occurred; i.e. the % necroses are determined, with 100% necrosis corresponding to a complete destruction of the plant. Solvent effects, as far as present, are compensated by means of the "Abbott formulan. The results are compiled in the following Table.
Table I (% necrosis) S Active ingredient Dosage Alopecurus Digitaria Avena g/ha myosuroides floridana fatua Compound A 312 100 100 100 A = 2-/ p-~(a,a,a-Trifluoro-p-tolyl)oxy]phenoxy_7-propionic acid ~ [(isopropylideneamino)oxy]methyl_7 ester.
Example 10 Table II
% Necrosis in cotton var. Stoneville 7A
kg/ha Compound A Compound H
1.25 0 22 0.62 0 _ _ }0 Formulation: Active ingredient250 g/l NMP 300 g/l Tensiofix B 7425100 g/l Phenylsulphonate CA 25 g/l Shellsol ABad 1000 ml Wetting agent: 0.08~ of Nonoxynol Growth staqe at treatment: 2 leaf stage SpraY volume: 1000 l/ha ApPraisal: 10 days after treatment Location: Greenhouse Compound A see Example 9 Compound H = D-2-[p-(p-Trifluoromethylphenoxy)phenoxy]--propionic acid methyl ester.
Example 11 Table III
% Necrosis in soYa beans var. ~ood ¦kgo/hagae ¦ Compound A ¦
1.25 0 0.62 0 Formulation: Active ingredient 250 g/l NMP 300 g/l Tensiofix B 7425100 g/l Phenylsulphonate CA 25 g/l Shellsol ABad 1000 ml Wettinq aqent: 0.08~ of Nonoxynol Growth stage at treatment: 2 trifoliate leaf SpraY volume: 1000 l/ha Appraisal: 2 weeks after treatment Location: Greenhouse Compound A see Example 9.
The notations NMP, Tensiofix B 7425, Phenyl-sulphonate CA, Shellsol AB and Nonoxynol used in Examples ~0 and 11 have the following significance:
NMP: N-methyl-2-pyrrolidone, Tensiofix B 7425: Emulsifier consisting of 60 parts of a block polymerisate of ethylene oxide and propylene oxide, 20 parts of the calcium salt of a branched-chain dodecylbenzenesulphonic acid and 20 parts of a solvent mixture of isobutanol and C10--alkylbenzenes.
Phenylsulphonate CA: Mixture of 70 par~s of the calcium salt of a branched-chain dodecylbenzenesulphonic acid and 3~ parts of a solvent mixture of isobutanol and C10-alkylbenzenes .
Shellsol AB: Solvent consisting of a mixture of C10-alkylbenzenes.
Nonoxynol: Condensation product of nonylphenol and ethylene oxide.
[a]D = +6.86 (c = 2.73% in chloroform);
lS from D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy /--propionic acid ~(methylsulphonyl)methyl} ester and benzaldoxime sodium salt there is obtained ~-2-~ p--[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7-propionic acid ~ [(benzylideneamino)oxy]methyl 7 ester; melting point 65-66C; [alD = -16.34 (c = 1.60~ in chloroform);
from D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy_7--propionic acid [(methylsulphonyl)methyl] ester and ethyl methyl ketoxime sodium salt there is obtained D-2-l p-~(a,a,a-trifluoro-p-tolyl)oxy]phenoxy_7--propionic acid ~ t(sec.butylideneamino)oxy]methyl_7 ester; melting point 38-40C; [a}D2 = + 10.34 (c = 2.36% in chloroform);
from D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy_/--propionic acid ~(methylsulphonyl)methyl] ester and dipentyl ketoxime ~x~ t ~ ~ d~Ed ~2-~(a,a,~
-trifluoro-p-tolyl)oxy]-phenoxy 7-propionic acid ~ ~(l-pentyl-hexylideneamino)oxy] methyl 7 ester;
nD = 1.4913; ~a]D2 = ~11.71 (c = 3.27% in chloroform);
from D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid [(methylsulphonyl)methyl] ester and methyl (2-methyl-1-propenyl) ketoxime sodium salt there is obtained D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]-phenoxy_7-propionic acid ~ [~1,3-dimethyl-2-buten-ylideneamino)oxy]methyl 7 ester; melting point 52 -54 C; [a~D = -5.7S (c = 0.78% in chloroform~.
}0 Example 2 A solution of 10 g (0.0307 mol) of D-2-/ p-t(Q,a,a--trifluoro-p-tolyl)oxy]phenoxy 7-propionic acid in 100 ml of dimethylformamide is added dropwise while stirring S to a suspension of l.S g of 55% sodium hydride dispersion (0.0307 mol) in 20 ml of dimethylformamide. After completion of the addition, the mixture is stirred at room temperature until the hydrogen evolution has stopped. The mixture is stirred for a further lS minutes and there are added thereto 15 g (0.048 mol) of N-[(iso-propylideneamino)oxy]-N-methyl-piperidinium iodide and 0.5 g of lS-crown-5 (the polyethylene ether-crown compound with a 15-ring containing ~ oxygen atoms). After stirring at 110C for 2 hours, the mixture is poured into 500 ml of water and extracted three times w~th 300 ml of ethyl acetate each time. The ethyl acetate extracts are combined, washed twice with 200 ml of water each time and then evaporated, the residue being subsequently recrysta}lised from diethyl etherJn-hexane. There are o~tained 8,o g of D-2-/ p-~(a,a,a-trifluoro-p-tolyl)oxy~-phenoxy_~-propionic acid / ~(isopropylideneamino)oxyl-}V
methyl_/ ester which melts at 85-86C; [a]20 = +11~3 (c = 1.2% in chloroform).
Example 3 1.75 g of L ~-)-lactic acid ~ ~(isopropylideneamino)-oxy~methyl / ester, 2.65 g of triphenylphosphine and 2.54 g of p-[(a,a,a-trifluoro-p-tolyl)oxy~-phenol are dissolved at 0C in 10 ml of absolute tetrahydrofuran.
1.75 g of azodicarboxylic acid diethyl ether are added dropwise to the solution while cooling. After completion of the addition, the mixture is stirred for 0.5 hour, then poured into 100 ml of water, extracted twice with 50 ml of water each time, dried over anhydrous sodiium sulphate and evaporated. The residue is chromatographed on a 20-fold amount of silica gel with n-hexane/ethyl acetate (4:1) and the eluate is evaporated. The residue is crystallised from diethyl ether/n-hexane and there is obtained D-2-/ p-~( a, a, a- trif}uoro-p-tolyl)oxy~phenoxy ? ~
-propionic acid / [(isopropylideneamino)oxy~methyl_/
ester; melting point 85~C; ~a~D = flO.9 ~c = 1.33%
in chloroform).
II. Preparation of the startinq materials:
ExamPle 4 100 g(0.03 mol) of 2-~ p-~(a,a,-trifluoro-p--tolyl)oxy]-phenoxy 7-propionic acid and 252 g (3.0 mol) of sodium bicarbonate are suspended in 2.5 litres of dimethyl sulphoxide and thereafter treated slowly with 336.5 ml (3.0 mol) of tert.butyl bromide. The mixture is stirred at room temperature overnight. The mixture, including the separated thick precipitate, is subsequently taken up in 5 litres of ethyl acetate. The ethyl acetate solution is washed twice with 1 litre of water, dried over sodium sulphate and evaporated. The residue is chromatographed on a 10-fold amount of silica gel with hexane/ethyl acetate (7:1) and the eluate is evaporated. There is obtained 2-l p-[(a,a,a-trifluoro--p-tolyl)oxyl phenoxy /-propionic acid [(methylthio)-methyl3 ester in the form of an oil.
40 g (0.096 mol) of 2-~ p-[( a,a,a-trifluoro-p--tolyl)oxy] phenoxy 7-propionic acid ~ (methylthio)-methyl3 ester are dissolved in 120 ml of acetone/water (5:1) and treated slowly with 192 ml of a 30% solution of hydrogen peroxide. 96 ml of ammonium molybdate solution (35.2 g of ammonium molybdate in 96 ml of water) are added dropwise to the mixture which is cooled with an ice-bath. The mixture is stirred at room temperature for 2 hours. It is .then extracted several times with ether, the ether extract is washed with sodium dithionite solution and the solution is again washed neutral with eight 100 ml portions of saturated sodlum chloride solution and subsequently with five 100 ml portions of water. The mixture is treated with active carbon, filtered and e~aporated.
The residue is recrystallised from methylene chloride/
n-hexane. There is obtained 2-/ p-[(,a,a-trifluoro--p-tolyl)oxy~phenoxy_7-propionic acid ~(methylsulphonyl)-methyl] ester which melts at 87-88C.
In a manner analogous to that described in the first paragraph of thls Example, from D-2-~ p-t(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid there is obtained D-2-~ p-[(a,a,a--trifluoro-p-tolyl)oxy~phenoxy 7-propionic acid ~(methylthio)methyl] ester; melting point 47-48C;
~a]D2= +31.24 (c = 1.58% in chloroform);
from D-2-[p-(p-chlorophenoxy)phenoxy]-propionic acid there is obtained D-2-[p-(p-chlorophen~xy)-phenoxy]-propionic acid [(methylthio) methy~] ester;
melting point 75C; [a]D2= + 50.54 (c = 1.34% in chloroform);
from 2-~p-(o,p-dichlorophenoxy)phenoxy~-propionic acid there is obtained 2-~p-(o,p-dichlorophenoxy)-phenoxy]-propionic acid [(methylthio)methyl] ester;
melting point 54C;
from D-2-[p-(p-bromophenoxy)phenoxyl-propionic acid there is obtained 2-[p-(o,p-dichlorophenoxy)-phenoxyl-propionic acid [(methylthio)methyl] ester;
melting point 83-87C; [~322 = +45.52 (c = 1.81%
in chloroform);
from D-2-[p-(p-iodophenoxy3phenoxy~-propionic acid there is obtained D-2-[p-(p-iodophenoxy)phenoxy~--propionic acid ~(methylthio)methyl~ ester; melting point 71-74C; [a]22 = +41.39 (c = 1.43% in chloroform);
In a manner analogous to that described in the second paragraph of this Example, from D-2-L p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy_7--propionic acid [(methylthio)methyl] ester there is obtained D-2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid ~(methylsulphonyl)methyl] ester;
melting point 79-82C; ~3DO = +40 77 (c = 1.66%
in chloroform);
from 2-~ p-~(a,a,a-trifluoro-p-tolyl)oxy]phenoxy_7--propionic acid [(phenylthio)methyl ester there is obtained 2-l p-~(a,a,a-trifluoro-p-tolyl)oxy]phenoxy 7--propionic acid ~(phenylsulphonyl)methyll ester;
melting point 89-92C;
from D-2-[p-(p-chlorophenoxy)phenoxy]-propionic acid [(methylthio)methyl] ester there is obtained D-2-[p-(p-chlorophenoxy)phenoxy]-propionic acid [(methylsulphonyl)methyl] ester; melting point 81-83C; ~a]D2= +43.42 (c = 1.02% in chloroform);
from 2-[p-(o,p-dichlorophenoxy)phenoxy]-propionic acid [(methylthio)methyl] ester there is obtained 2-[p-(o,p-dichlorophenoxy)phenoxy3-propionic acid [(methylsulphonyl)methyll ester; melting point 95C;
from D-2-tp-(p-bromophenoxy)phenoxy]-propionic acid r (methylthio)methyl~ ester there is o~tained D-2-[p-(p-bromophenoxy)phenoxy]-propionic acid [(methylsulphonyl)methyl] ester; melting point 84-87C; [a]D2= +39.20 (c = 1.43~ in chloroform);
from D-2-[p-(p-iodophenoxy)phenoxy3-propionic acid - [(methylthio)methyl] ester there is obtained D-2-[p--(p-iodophenoxy)phenoxy]-propionic acid ~(methylsulphonyl)-methyl] ester; melting point 121~-123~C; ~a3D2= +37,9t (c = 2.66~ in chloroform).
l~z~
Example 5 153 ml (1.1 mol) of tert.butyl bromide are slowly added dropwise to a suspension of 10 g (0.11 mol) of L (+)-lactic acid and 94.2 g (1.1 mol) of sodium bicarbonate in 200 ml of dimethyl sulphoxide. The mixture is stirred for 48 hours, then poured into 1 litre of water and extracted twice with 100 ml of ethyl acetate each time. The organic phase is back-washed three times with 200 ml of water each time and subsequently evaporated. The crude product is chromatographed on a 20-fold amount of silica gel with n-hexane/ethyl acetate (4:1) and the eluate is evaporated. There are obtained 5.7 g of L (-)-lactic acid ~(methylthio)methyl] ester;
[a]20 = -39.27 (c = 1.3~ in chloroform).
The foregoing ester can also be obtained by heating 11.2 g of L (+)-sodium lactate, 0.5 g of 1 ~crown-5, 9.25 g of chlorodimethyl sulphide and a trace of sodium iodide in 100 ml of absolute acetonitrile at the reflux temperature of the mixture. After 6 hours, the mixture is poured into water and worked-up in the manner 5'~0 described in the preceding paragraph. There are obtained 6.1 g of L (-)-lactic acid ~(methylthio)-methyl] ester; ~a]20 = _ 3 8.5 (c = 0.69% in chloroform).
2.55 g (0.01 mol) of p-~(~,a,a-trifluoro-p-tolyl)-ox~lphenol, 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 mixture is cooled to 0C. While cooling there is added dropwise 0.011 mol of azodicar~oxylic acid diethyl ester, the yellow colour of this ester disappearing during the addition. The mixture is then stirred at room temperature for 30 minutes, poured into 100 ml of water, extracted twice with 50 ml of ethyl acetate each time and the organic lS phase is washed neutral with water. The ethyl acetate solution is then evaporated, the residue is chromatographed on a 20-fold amount of silica gel with n-hexane/ethyl acetate (9:1) and the eluate is evaporated. After crystallisation from diethyl ether/n-hexane, there are obtained 2.1 g of D-2-/ p-~(a,~ trifluoro-p-tolyl)oxyl-phenoxy 7-propionic acid ~(methylthio)methyll ester;
meltins point 52C; ~a~20 = +46.87~ (c = 0.65% in chloroform).
Example 6 To 100 ml of 36% formalin at 10C are added dropwise while cooling 100 ml of piperidine and t~ereupon 73 g of acetone oxime as well as 75 g of potassium carbonate. The mixture is stirred at room temperature overnight, then taken up in ethyl acetate and the aqueous phase is separated. The organic phase is evaporated, the residue is taken up in acetone and treated dropwise while cooling with 6S ml of methyl iodide, whereafter the product slowly crystallises out.
After a further 10 hours, the product is filtered off.
There are obtained 291 g of N-[(isopropylideneamino)oxy]--N-methyl-piperidinium iodide; melting point 132-133C.
Example 7 1.1 g of sodium lactate, 3.5 g of N-[(isopropylidene-amino)oxy~-N-methyl-piperidinium iodide and 0.1 g of 1 ~
-crown-5 in 10 ml of diglycol dimethyl ether are heated at 110C under nitrogen for 4 hours. The mixture is then poured into 50 ml of water and extracted three times with ethyl acetate. The organic phase is washed four times with water and subsequently evaporated. After chromatography of the residue on a 10-fold amount of silica gel with n-hexane/ethyl acetate (1:1) and evaporation of the elua~e, there is obtained 0.35 g of L (-)-lactic acid ~ ~(isopropylideneamino)oxy3methyl_7 ester; [a]20 = -1.2 (c = 1.50% in chloroform).
I}I. Formulation Examples-ExamPle 8 - An emulsifiable concentrate is produced by mixing the following ingredients with one another:
Compound of formula I S00 g Condensation product of an alkylphenol and ethylene oxide; calcium dodecyl-benzenesulphonic acid 100 g Epoxidated soya oil with an oxirane oxygen content of about 6% 25 g Butylated hydroxytoluene 10 g This mixture is made up to l litre with xylene.
Example 9 The active ingredient of formula I, for example 2-~ p-[(a,a,a-trifluoro-p-tolyl)oxy~phenoxy_7-propionic acid ~ ~tisopropylideneamino)oxy]methyl 7 ester (compound A ~n the following Table ) is dissolved in acetone to give a 2% solution of active ingredient.
Shortly before the beginning of the experiment the solution is diluted with water to provide the desired concentration, which in the present experiment is 312 g/ha.
(When an insoluble active ingredient is used, spray powders which contain kaolin as the inert diluent are formulated.1 The test plants are sprayed in a greenhouse with the formulated active ingredient, a 16 hours day being simulated by means of mercury vapour lamps. 3 weeks after the spraying the plants are examined for the effects which have occurred; i.e. the % necroses are determined, with 100% necrosis corresponding to a complete destruction of the plant. Solvent effects, as far as present, are compensated by means of the "Abbott formulan. The results are compiled in the following Table.
Table I (% necrosis) S Active ingredient Dosage Alopecurus Digitaria Avena g/ha myosuroides floridana fatua Compound A 312 100 100 100 A = 2-/ p-~(a,a,a-Trifluoro-p-tolyl)oxy]phenoxy_7-propionic acid ~ [(isopropylideneamino)oxy]methyl_7 ester.
Example 10 Table II
% Necrosis in cotton var. Stoneville 7A
kg/ha Compound A Compound H
1.25 0 22 0.62 0 _ _ }0 Formulation: Active ingredient250 g/l NMP 300 g/l Tensiofix B 7425100 g/l Phenylsulphonate CA 25 g/l Shellsol ABad 1000 ml Wetting agent: 0.08~ of Nonoxynol Growth staqe at treatment: 2 leaf stage SpraY volume: 1000 l/ha ApPraisal: 10 days after treatment Location: Greenhouse Compound A see Example 9 Compound H = D-2-[p-(p-Trifluoromethylphenoxy)phenoxy]--propionic acid methyl ester.
Example 11 Table III
% Necrosis in soYa beans var. ~ood ¦kgo/hagae ¦ Compound A ¦
1.25 0 0.62 0 Formulation: Active ingredient 250 g/l NMP 300 g/l Tensiofix B 7425100 g/l Phenylsulphonate CA 25 g/l Shellsol ABad 1000 ml Wettinq aqent: 0.08~ of Nonoxynol Growth stage at treatment: 2 trifoliate leaf SpraY volume: 1000 l/ha Appraisal: 2 weeks after treatment Location: Greenhouse Compound A see Example 9.
The notations NMP, Tensiofix B 7425, Phenyl-sulphonate CA, Shellsol AB and Nonoxynol used in Examples ~0 and 11 have the following significance:
NMP: N-methyl-2-pyrrolidone, Tensiofix B 7425: Emulsifier consisting of 60 parts of a block polymerisate of ethylene oxide and propylene oxide, 20 parts of the calcium salt of a branched-chain dodecylbenzenesulphonic acid and 20 parts of a solvent mixture of isobutanol and C10--alkylbenzenes.
Phenylsulphonate CA: Mixture of 70 par~s of the calcium salt of a branched-chain dodecylbenzenesulphonic acid and 3~ parts of a solvent mixture of isobutanol and C10-alkylbenzenes .
Shellsol AB: Solvent consisting of a mixture of C10-alkylbenzenes.
Nonoxynol: Condensation product of nonylphenol and ethylene oxide.
Claims (24)
1. Compounds of the general formula I
wherein Rl represents a hydrogen atom, an alkyl group containing 1-6 carbon atoms or a phenyl group, R2 represents an alkyl group containing 1-6 carbon atoms, an alkenyl group containing 2-6 carbon atoms, an alkynyl group containing 2-6 carbon atoms or a phenyl group or R1 and R2 together with the carbon atom to which they are attached form a cycloalkane ring containing 4-10carbon atoms which, if desired, can be mono-di- or tri-substituted with alkyl containing 1-3 carbon atoms, R3 represents a halogen atom or a trifluoromethyl or nitro group and R4 and R5 each represent a hydrogen or halogen atom.
wherein Rl represents a hydrogen atom, an alkyl group containing 1-6 carbon atoms or a phenyl group, R2 represents an alkyl group containing 1-6 carbon atoms, an alkenyl group containing 2-6 carbon atoms, an alkynyl group containing 2-6 carbon atoms or a phenyl group or R1 and R2 together with the carbon atom to which they are attached form a cycloalkane ring containing 4-10carbon atoms which, if desired, can be mono-di- or tri-substituted with alkyl containing 1-3 carbon atoms, R3 represents a halogen atom or a trifluoromethyl or nitro group and R4 and R5 each represent a hydrogen or halogen atom.
2. Compounds according to claim 1, wherein the cycloalkane ring contains 4-6 carbon atoms.
3. Compounds according to claim 2, wherein R1 represents a methyl or ethyl group.
4. Compounds according to claim 2, wherein R2 represents a methyl, ethyl or phenyl group.
5. Compounds according to claim 3, wherein R2 represents a methyl, ethyl or phenyl group.
6. Compounds according to any one of claims 2 to 4, wherein R3 represents a chlorine atom or a trifluoromethyl group.
7. Compounds according to any one of claims 2 to 4, wherein R4 represents a hydrogen atom.
8. Compounds according to any one of claims 2-4, wherein R5 represents a hydrogen atom.
9. 2-[ p-[(.alpha.,.alpha.,.alpha.-Trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(isopropylideneamino)oxy]methyl ]
ester.
ester.
10. 2-[p-(p-Chlorophenoxy)phenoxy]-propionic acid [ [(isopropylideneamino)oxy]methyl ] ester.
11. A compound according to claim 2 selectad from:
D-2-[ p-[(.alpha.,.alpha.,.alpha.-Trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(isopropylideneamino)oxy]methyl ]
ester, D-2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]phenoxy ]
-propionic acid [ [(.alpha.-methyl-benzylideneamino)oxy]-methyl ] ester, D-2-[p-(p-chlorophenoxy)phenoxy]-propionic acid (isopropylideneamino)oxy]methyl ] ester, 2-[p-(o,p-dichlorophenoxy)phenoxy]-propionic acid [ [(isopropylideneamino)oxy]methyl ] ester, 2-[p-(o,p-dichlorophenoxy)phenoxy]-propionic acid [ [(.alpha.-methyl-benzylideneamino)oxy]methyl ] ester, D-2-[p-(p-bromophenoxy)phenoxy]-propionic acid [ [(isopropylideneamino)oxy] methyl ] ester, D-2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(cyclopentylideneamino)oxy]methyl ]
ester, D-2-[p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(cyclohexylideneamino)oxy]methyl ]
ester, D 2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(benzylideneamino)oxy]methyl ] ester, D-2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(sec.butylideneamino)oxy]methyl ]
ester and D-2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(1-pentyl-hexylideneamino)oxy]methyl ]
ester.
D-2-[ p-[(.alpha.,.alpha.,.alpha.-Trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(isopropylideneamino)oxy]methyl ]
ester, D-2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]phenoxy ]
-propionic acid [ [(.alpha.-methyl-benzylideneamino)oxy]-methyl ] ester, D-2-[p-(p-chlorophenoxy)phenoxy]-propionic acid (isopropylideneamino)oxy]methyl ] ester, 2-[p-(o,p-dichlorophenoxy)phenoxy]-propionic acid [ [(isopropylideneamino)oxy]methyl ] ester, 2-[p-(o,p-dichlorophenoxy)phenoxy]-propionic acid [ [(.alpha.-methyl-benzylideneamino)oxy]methyl ] ester, D-2-[p-(p-bromophenoxy)phenoxy]-propionic acid [ [(isopropylideneamino)oxy] methyl ] ester, D-2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(cyclopentylideneamino)oxy]methyl ]
ester, D-2-[p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(cyclohexylideneamino)oxy]methyl ]
ester, D 2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(benzylideneamino)oxy]methyl ] ester, D-2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(sec.butylideneamino)oxy]methyl ]
ester and D-2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(1-pentyl-hexylideneamino)oxy]methyl ]
ester.
12. A compound according to claim 1 selected from:
D-2-[p-(p-Iodophenoxy)phenoxy]-propionic acid [ [(isopropylideneamino)oxy]methyl ] ester, D-2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(3,3,5-trimethylcyclohexylideneamino)-oxy]methyl ] ester and D-2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(1,3-dimethyl-2-butenylideneamino)-oxy]methyl ] ester.
D-2-[p-(p-Iodophenoxy)phenoxy]-propionic acid [ [(isopropylideneamino)oxy]methyl ] ester, D-2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(3,3,5-trimethylcyclohexylideneamino)-oxy]methyl ] ester and D-2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]phenoxy ]--propionic acid [ [(1,3-dimethyl-2-butenylideneamino)-oxy]methyl ] ester.
13. The D-isomers of the compounds of formula I given in claim 1.
14. The D-isomers of the compounds of formula I
according to any one of claims 2 to 4.
according to any one of claims 2 to 4.
15. The D-isomers of the compounds of formula I.
according to claim 5.
according to claim 5.
16. A process for the manufacture of compounds of the general formula I
wherein R1 represents a hydrogen atom, an alkyl group containing 1-6 carbon atoms or a phenyl group, R2 represents an alkyl group containing 1-6 carbon atoms, an alkenyl group containing 2-6 carbon atoms, an alkynyl group containing 2-6 carbon atoms or a phenyl group or R1 and R2 together with the carbon atom to which they are attached form a cycloalkane ring containing 4-10 carbon atoms which, if desired, can be mono-, di-or tri-substituted with alkyl containing 1-3 carbon atoms, R3 represents a halogen atom or a trifluoromethyl or nitro group and R4 and R5 each represent a hydrogen or halogen atom, which process comprises (a) reacting a salt of an acid of the general formula II
wherein R3, R4 and R5 have the significance given earlier in this claim, with a compound of the general formula wherein R1 and R2 have the significance given earlier in this claim and X represents a leaving group, or (b) reacting a compound of the general formula IV
wherein Z represents a leaving group and R1 and R2 have the significance given earlier in this claim, with a compound of the general formula V
wherein R3, R4 and R5 have the significance given earlier in this claim or with an alkali metal salt thereof, or (c) reacting a compound of the general formula VI
wherein R6 represents a lower alkyl, an aryl or a heteroaryl group and R3, R4 and R5 have the significance given earlier in this claim, with a compound of the general formula wherein R1 and R2 have the significance given earlier in this claim, or with an alkali metal salt thereof in the presence of a base.
wherein R1 represents a hydrogen atom, an alkyl group containing 1-6 carbon atoms or a phenyl group, R2 represents an alkyl group containing 1-6 carbon atoms, an alkenyl group containing 2-6 carbon atoms, an alkynyl group containing 2-6 carbon atoms or a phenyl group or R1 and R2 together with the carbon atom to which they are attached form a cycloalkane ring containing 4-10 carbon atoms which, if desired, can be mono-, di-or tri-substituted with alkyl containing 1-3 carbon atoms, R3 represents a halogen atom or a trifluoromethyl or nitro group and R4 and R5 each represent a hydrogen or halogen atom, which process comprises (a) reacting a salt of an acid of the general formula II
wherein R3, R4 and R5 have the significance given earlier in this claim, with a compound of the general formula wherein R1 and R2 have the significance given earlier in this claim and X represents a leaving group, or (b) reacting a compound of the general formula IV
wherein Z represents a leaving group and R1 and R2 have the significance given earlier in this claim, with a compound of the general formula V
wherein R3, R4 and R5 have the significance given earlier in this claim or with an alkali metal salt thereof, or (c) reacting a compound of the general formula VI
wherein R6 represents a lower alkyl, an aryl or a heteroaryl group and R3, R4 and R5 have the significance given earlier in this claim, with a compound of the general formula wherein R1 and R2 have the significance given earlier in this claim, or with an alkali metal salt thereof in the presence of a base.
17. A process according to claim 16, wherein the cycloalkane ring contains 4-6 carbon atoms and X
and Z each represent a chlorine, bromine or iodine atom or a mesyloxy or tosyloxy group.
and Z each represent a chlorine, bromine or iodine atom or a mesyloxy or tosyloxy group.
18. A process according to claim 17 for the manufacture of 2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy] phenoxy]--propionic acid [ [(isopropylideneamino)oxy]methyl]
ester, wherein 2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]-phenoxy ]-propionic acid [(methylsulphonyl)methyl]
ester is reacted with acetone oxime sodium salt.
ester, wherein 2-[ p-[(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyl)oxy]-phenoxy ]-propionic acid [(methylsulphonyl)methyl]
ester is reacted with acetone oxime sodium salt.
19. A process according to claim 16, wherein the D-isomer of the starting material of formula VI is used.
20. A process according to claim 17 or claim 18, wherein the D-isomer of the starting material of formula VI is used.
21. A method for the control of weeds, which method comprises treating the locus to be protected against weeds and/or the weeds with an effective amount of a compound set forth in any one of claims 1, 12 or 13.
22. A method for the control of weeds, which method comprises treating the locus to be protected against weeds and/or the weeds with an effective amount of a compound set forth in any one of claims 2 to 4.
23. A method for the control of weeds, which method comprises treating the locus to be protected against weeds and/or the weeds with an effective amount of a compound set forth in any one of claims 5, 9 or 10.
24. A method for the control of weeds, which method comprises treating the locus to be protected against weeds and/or the weeds with an effective amount of a compound set forth in claim 11.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH11003/79 | 1979-12-12 | ||
| CH1100379 | 1979-12-12 | ||
| CH801880 | 1980-10-28 | ||
| CH8018/80 | 1980-10-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1142540A true CA1142540A (en) | 1983-03-08 |
Family
ID=25702656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000364790A Expired CA1142540A (en) | 1979-12-12 | 1980-11-17 | Propionic acid esters |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0030702B1 (en) |
| AU (1) | AU6511280A (en) |
| CA (1) | CA1142540A (en) |
| CS (1) | CS219297B2 (en) |
| DD (1) | DD154570A5 (en) |
| DE (1) | DE3064660D1 (en) |
| DK (1) | DK529580A (en) |
| ES (1) | ES497621A0 (en) |
| FI (1) | FI803873L (en) |
| GB (1) | GB2065649B (en) |
| IL (1) | IL61638A (en) |
| NO (1) | NO149351C (en) |
| RO (1) | RO82489A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA811357B (en) * | 1980-03-10 | 1982-03-31 | Hoffmann La Roche | Oxime esters |
| EP0054715A3 (en) * | 1980-12-18 | 1982-09-22 | F. HOFFMANN-LA ROCHE & CO. Aktiengesellschaft | Esters of propanoic acid, preparation of these compounds, weed killers containing these compounds as active ingredients, use of such compounds and compositions for the control of weeds |
| JPS58183666A (en) * | 1982-04-20 | 1983-10-26 | Nippon Tokushu Noyaku Seizo Kk | Substituted phenoxypropionic ester, intermediate for preparing the same, preparation of said ester and intermediate and herbicide |
| DK416583A (en) * | 1982-10-06 | 1984-04-07 | Hoffmann La Roche | BENZOIC ACID DERIVATIVES WITH HERBICIDE EFFECT |
| FI92189C (en) * | 1986-03-17 | 1994-10-10 | Eisai Co Ltd | A process for preparing a diphenylmethane derivative useful as a medicament |
| DE4131585A1 (en) * | 1991-09-23 | 1993-03-25 | Bayer Ag | (ALPHA) - (5-DICHLORPHENOXY-NAPHTHALIN-L-YL-OXY) PROPIONE ACID DERIVATIVES |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2223894C3 (en) * | 1972-05-17 | 1981-07-23 | Hoechst Ag, 6000 Frankfurt | Herbicidal agents based on phenoxycarboxylic acid derivatives |
-
1980
- 1980-11-17 CA CA000364790A patent/CA1142540A/en not_active Expired
- 1980-12-05 IL IL61638A patent/IL61638A/en unknown
- 1980-12-05 AU AU65112/80A patent/AU6511280A/en not_active Abandoned
- 1980-12-09 EP EP80107745A patent/EP0030702B1/en not_active Expired
- 1980-12-09 RO RO80102809A patent/RO82489A/en unknown
- 1980-12-09 DE DE8080107745T patent/DE3064660D1/en not_active Expired
- 1980-12-10 NO NO803729A patent/NO149351C/en unknown
- 1980-12-11 GB GB8039687A patent/GB2065649B/en not_active Expired
- 1980-12-11 CS CS808735A patent/CS219297B2/en unknown
- 1980-12-11 DD DD80225971A patent/DD154570A5/en unknown
- 1980-12-11 DK DK529580A patent/DK529580A/en not_active Application Discontinuation
- 1980-12-11 ES ES497621A patent/ES497621A0/en active Granted
- 1980-12-12 FI FI803873A patent/FI803873L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| ES8203337A1 (en) | 1982-04-01 |
| NO149351B (en) | 1983-12-27 |
| GB2065649B (en) | 1984-02-15 |
| EP0030702B1 (en) | 1983-08-24 |
| GB2065649A (en) | 1981-07-01 |
| NO803729L (en) | 1981-06-15 |
| ES497621A0 (en) | 1982-04-01 |
| DK529580A (en) | 1981-06-13 |
| RO82489B (en) | 1983-09-30 |
| DE3064660D1 (en) | 1983-09-29 |
| DD154570A5 (en) | 1982-04-07 |
| CS219297B2 (en) | 1983-03-25 |
| AU6511280A (en) | 1981-06-18 |
| RO82489A (en) | 1983-10-15 |
| EP0030702A1 (en) | 1981-06-24 |
| NO149351C (en) | 1984-04-04 |
| IL61638A (en) | 1984-06-29 |
| FI803873L (en) | 1981-06-13 |
| IL61638A0 (en) | 1981-01-30 |
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