CA1156663A

CA1156663A - Propionic acid esters

Info

Publication number: CA1156663A
Application number: CA000389700A
Authority: CA
Inventors: Georg Frater; Milos Suchy; Paul Winternitz
Original assignee: F Hoffmann La Roche AG
Current assignee: F Hoffmann La Roche AG
Priority date: 1980-12-18
Filing date: 1981-11-09
Publication date: 1983-11-08
Also published as: GB2091248A; ES8302631A1; EP0054715A2; IL64523A0; ES508104A0; NO814332L; FI814059L; EP0054715A3; DK561581A; AU7846381A; AR230429A1

Abstract

Abstract The invention is concerned with propionic acid esters of the formula I

wherein R1, R2, R3, R4, R5, m, n and p have the significance given in the description, a process for their manufacture, weed control compositions which contain these compounds as the active substance, as well as the use of such compounds or compositions for the control of weeds.

Description

The invention is concernedwith propionic acid esters of the general formula .

Rl_~0~0--CH--COO--(CH2~ (Cl: ) -RS

wherein Rl signifies chlorine, bromine~
iodine or trifluoromethyl, R signiies hydrogen, chlorine, bromine or iodine, 10R3 signifies hydrogen or Cl 4--alkyl, R4 signifies hydrogen; Cl 4--alkyl; or phenyl, optionally substituted with halogen, Cl 4-alkyl and/or nitro, whereby R3 and R4 together with the carbon atom to which Pa/19.10.81 .. ~; ~

. . . . . .. . .

they are attached can also form a C5_8-cycloalkane ring which, if desired, can be substituted with 1 to 3 Cl 4--alkyl groups, m, n and p signify the number O or 1 and R5 signifies one of the following groups (a~ - (f):

-NHCO-R (a) -NHSO2-R (b) ~\ 8 ~&yR
~N I (c) d~C~\R

~ R10 -N=C ~ 11 (d) -ON=C (e) \R13 oRl 4 -P (f) O \ OR15 ' ;`

' .: :.: -: .. .

' whereby in the above formulae of the groups (a) - (f) R6 si~nifies hydrogen; Cl 6--alkyl; Cl 4-haloalkyl: or phenyl, optionally substituted with halogen, Cl 4-alkyl and/
or nitro, R signifies Cl 6-alkyl~ or phenyl, optionally substituted with halogen, Cl 4-alkyl and/
or nitro, R8 and R9 stand for hydrogen or together signify a bond, trimethylene, tetramethylene,

2 butenylene or a lused benzene ring, RlOsignifies Cl 6-alkyl and R
signifies trifluoromethyl, Cl_6 alkoxy, Cl-6-alkoxy--Cl_4-alkyl, C2_7-alkanoyl, C2 7-alkoxycarbonyl or C2 7--alkoxycarbonyl-Cl 4-alkyl, or R and Rll together with the carbon atom to which they are attached form a cyclopentane ring which, if desired, can be . . . --~

,, .

-"~ 1156~3 substituted with 1 to 3 Cl 4-alkyl sroups and/or 1 Cl_4-alkoxy group, whereby, where R , R and the carbon atom form an optionally substituted cyclopentane ring, Rl is chlorine, bromine or trifluoromethyl, R12 signifies hydrogen or Cl 6--alkyl and R13 signifies Cl_6-alkyl; or phenyl, optionally substituted with halogen, Cl 4-alkyl and/or nitro, or R12 and R13 together with the carbon atom to which they axe attached form a C5_7-cycloalkane ring, and Rl and R15 signify Cl 6-alkyl or phenyl, and whereby, when R5 represents a group (a), (b) or (c), m signlfies the number 1, n signifies the number 0 and p signifies the number 0 or 1; when R5 repre ents a group (d), m, n and p signif~ the number 0; when R5 represents a group (e), m signifies the . .

1 ~ 3 number 0 and n and p signify the number . l; and when R represents a group (f), m and p signify the number 0 or 1 and n signifies the number 1.

The compounds of formula I possess herbicidal properties and are accordingly suitable as weed control agents and as active substances of weed control compositions. Accordingly, the invention also lncludes weed co~trol compositions which contain at least one compound of formula I as the active substance, a process for the manufacture of these compounds as well as the use of such compounds or compositions for th~ control of weeds.

In formula I above the term "halogen" includes fluorine, chlorine, bromine and iodine. The term "Cl_4-alkyl" or "Cl_6-alkyl" means not only straight--chain but also branched-chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert.butyl, n-pentyl, isoamyl, neo-pentyl and n-hexyl. This is also true for groups containing C1 4-alkyl groups or Cl_6--alkyl groups such as Cl_4- or Cl_6-alkoxy, C2_7-alkoxy-carbonyl, Cl 4-haloalkyl, C2 7-alkoxycarbonyl-C1 4-alkyl, Cl_6-alkoxy-Cl_4-alkyl and C2_7-alkanoyl. When two or more substituents are present in a substituted phenyl group, the substituents can be the same or different.
This is also true for the C5 8-cycloalkane ring substituted with alkyl and the cyclopentane ring substituted with alkyl and/or alkoxy. The term "haloalkyl"
includes alkyl substituted with one or more halogen atoms.

Since at least one asymmetric carbon atom is present in the molecule, the compounds of formula I can occur in optically active form. As a conse~uence of the nitrogen-carbon double bond in the compounds of ~ormula I in which R5 signifies a group (d) or a group ~e) geometric isomerism also occurs in the case of those compounds in which R and Rll or R12 and R13 have different significances. Such geometric isomers are called the syn- and anti-forms~ Inde~endently thereof, an atropic isomerism is also present in certain cases.
Formula I is accordingly intended to include the racemates as well as all of these possible isomeric forms.

Independently of one another R preferably signifies iodine or trifluoromethyl and R2 preferably signifies hydrogen or chlorine.

When R signifies Cl 4-alkyl, this is preferably methyl.

: ~ ' .
~, .

1 156~3 R6 preferably signifies Cl 6-alkyl.

R7 preferably signifies optionally substituted phenyl.

R8 and R9 both preferably signify hydrogen.

The D-forms of the compounds of formula I are especially preferred.

Preferred compounds of formula I are:

Succinimidomethyl D-2-[p-(a,a,a-trifluoro-p--tolyloxy)phenoxy]-propionate, ethyl N-/ D-2-[p-(a,a,a-trifluoro-p~tolyloxy)-phenoxy]propionoxy_/-acetamidate, n-butyl N- r D-2-[p-(a,a,a-trifluoro-p-tolyloxy)- :
phenoxy]propionoxy ~ -acetimidate, 2-isopropylideneaminooxy-ethyl ~-2-[p-(a,a,a--trifluoro-p-tolyloxy)phenoxy]-propionate and diethoxyphosphinylmethyl D-2-[p-(a,a,a~trifluoro-p--tolyloxy)phenoxy]-propionate.

The process in accordance with the invention for the manufacture of the compounds of formula I comprises .

,, : ;, - : :

, 115~3 (a) reacting an acid of the formula R1 ~ O ~ CH3 , R2 wherein Rl and R2 have the significance given above, or a reactive derivative thereof, with a compound of the formula X- (CH2)m -(I)n (C 2)p - III

wherein R3, R4, R5, m, n and p have the significance given above and X signifies a leaving group, or :
(b) xeacting a phenol of the formula , " . . :

6~3 g R1 ~ O ~ OH IV

wherein Rl and ~2 have the significance given above, or an alkali metal salt thereof, with a compound of the formula Y- CH- COO -(CH2)m - (C)n -(CH2)p R V

wherein R , R , R , m, n and p have the significance given above and Y signiries a leaving group.

Process variant (a) is an esterification which can be carried out according to methods known per se;
for example, in accordance with the following variants (a1), (a2) and (a3): .

~ , .. .

Educt Rea~ent (al) Free acid of formula II, Compound of formula but especially a salt III in which X stands thereof for example, for chlorine, bromine, iodine, mesyloxy or tosylo~y (a2) Halide, imidazolide or Compound of Eormula anhydride of an acid of III in which X stands formula II for hydroxy (a3) Free acid of formula Compound of formula II III in which X stands for hydroxy (III
especially = oxime) In process variant (al), the term "salt" signifies, for example, an alkali metal salt (e.g. the sodium, potassium or lithium salt), an alkaline earth metal sal~ `
(e.g. the magnesium, calcium or barium salt), a salt of an organic base ~e.g. a mono-, di- or trialkylammonium salt or a pyridinium salt) or the ammonium salt. The term "leaving groupl' used in connection with X preferably stands for chlorine, bromine, iodine, mesyloxy or tosyloxyO

The esterification of an acid of formula II or, preferably, a salt thereof, with a compound of formula III is preferably carried out in an inert solvent and at a temperature of about -20C to 100C. A temperature i . , : :: ~: , .::
.,~ .

11~6~3 range between 0C and 40C is especially preferred.
Inert organic solvents are preferably used as the solvent.
Preferred solvents are ethers (e.g. diethyl ether and tetrahydrofuran), chlorinated hydrocarbons (e.g.
dichloromethane and chloroform~ and dimethylformamide.

When a free acid of formula II is used, the reaction is conveniently carried out in -the presence o~
a base or an acid acceptor. For this purpose there can be used all customarily usable inorganic and organic acid-binding agents, preferably alkali metal and alkaline earth metal carbonates and bicarbonates and tertiary amines (e.g. triethylamine, dimethylaniline and pyridine).

The reaction according to process variant (a2) is conveniently carried out in an inert solvent such as an ether (e.g. diethyl ether~, a hydrocarbon (e.g.
- n-hexane)or a chlorinated hydrocarbon (e.g. dichloro methane or chloroform) and at room temperature or an elevated temperature (e.g. up to the reflux temperatuxe of the reaction mixture). A temperature range between 0C and 40C is preferred and a temperature range between 10C and 20C is especially preferred.

When an acid halide of an acid of formula II is used, the reaction is conveniently carried out in the presence of an acid-binding agent. Inorganic bases (e~g.

.: .- . - , . . .

" , : ~ .

~: , 8~3 alkali metal and alkaline earth metal carbonates and bicarbonates) as well as organic bases (e.g. tertiary amines, especially triethylamine or pyridine) have been found to be suitable for this purpose. The acid h~lide is preferably the acid chloride.

In process variant (a3), the reaction is conveniently carried out in an inert organic solvent such as an ether (e.g. tetrahydrofuran) or a chlorinated hydrocarbon (e.g. dichloromethane or chloroform) and at a temperature between 0C and 70C. A temperature range between 10C and 30C is preerred. The reaction is conveniently carried out in the presence of an acid catalyst or a condensing agent such as, for example, sulphuric acid, hydrochloric acid, p-toluenesulphonic acid, dicyclohexylcarbodiimide or carbonyldiimidazole.

Process variant (a3) is especially suitable where the compound of formula III is an oxime, i.e. R5 signifies a group (d), m, n and p signify the number 0 and X signifies a hydroxyl group. An acid of formula II
is preferably reacted with an oxime of formula III in the presence of dicyclohexylcarbodiimide as the condensing agent. The acid is conveniently dissolved in an inert organic solven-t such as a chlorinated hydrocarbon (e.g. dichloromethane, chloroformr carbon tetrachloride or : .
, ~ ,' :: :
: . ,~ , ;

trichloroethane), an ether (e.g. diethyl ether, diisopropyl ether or dioxan) or an aromatic hydrocarbon (e.g. benzene, toluene or xylene) and thereafter the oxime is suspended in the solution. The dicyclohexylcarbodiimide is like~
wise dissolved in the same solvent and added to the -reaction mixture. The reaction is preferably carried out in a temperature range between 0C and the boiling point of the reaction mixture, especially between room temparature and 50C. The reaction is normally completed after about 2 hours.

In process variant (b), the term "leaving group"
used in connection with Y signifies, for example, chlorine, bromine, iodine, mesyloxy or tosyloxy. The reaction is conveniently carried out in an inert organic solvent such as a hydrocarbon (e.g. benzene or toluene~, an ether (e.g. diethyl ether, dimethoxyethane or tetrahydrofuran) or hexamethylphosphoric acid triamide. The reaction temperature is not critical and the reaction is preferably - carried out at a temperature between -20C and the reflux temperature of the reaction mixture, especially at a temperature between -10C and 30C.

~In each case the product obtained can be isolated and purified according to methods known per se.

. .:
- . ~ ; i :
.
- . ~. , . J

I 1~6~3 Insofar as no planned synthesis for the isolation of pure isomers is carried out, the product normally occurs as a mixture of two or more isomers. The isomers can be separated according to methods known per se. If S desired, they can also be manufactured by synthesis from corresponding optically active starting materials.

The starting materials of formulae II, III, IV
and V as well as reactive derivatives of the acids of formula II and alkali metal salts of the phenols of formula IV are either known or can be prepared in a manner known per se.

The compounds of formula I possess herbicidal properties and are especially suitable for the control of weed grasses, especially of slender foxtail (Alopecurus myosuroides) and types of millet 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 cultivations, as well as in rice, cotton, soya, sugar beet and vegetable plantations. The compounds in accordance with the invention are particularly suitable ~ for the control of weed grasses in cotton, soya, sugar beet and vegetable plantations.

.
, . - :

In general, a concentration of 001-6 kg of active substance of formula I per ha, preferably 0.6-2 kg of active substance of formula I per ha, is sufficient to produce the desired herbicidal effect.

The compounds o formula I are not only pre--emergence herbicides but also post-emergence herbicides.

The weed control compositions in accordance with the invention contain an effective amount of at least one compound of formula I, as defined above, as well as formulation adjuvants. Tha compositions conveniently contain at least one of the following formulation adjuvants: solid carrier substances; solvents or dispersion media ; tensides (wetting and emulsifying agents); d~si~ ~n~ (without tenside action); and stabilizers. When using these and other adjuvants the compounds o formula I, namely the herbicidal active substances, can be converted into the usual foxmulations such as dusts, powders, granulates~ solutions, emulsions, suspensions, emulsifiable concentrates, pastes and the like.

The compounds of formula I are generally insoluble in water and can be formulated according to the methods which are usual for water-insoluble compounds using the '' ` ':

. .:
. ~

respecti~e formulation adjuvant~ The manufacture of the compositions can be carried out in a manner known per se;
for example, by mixing the respective active substance with solid carrier substances, by dissolution or suspension in suitable solvents or dispersion media, if necessary using t~nsides as wetting or emulsifying agents and/or d~ i~ ~, by diluting pre-prepared emulsifiable concentrates with solvents or dispersion media etc.

As solid carrier substances there essentially come into consideration: natural mineral substances such as chalk, dolomite, limestone, aluminas and silicic acid and salts thereof (e.g. siliceous earth, kaolin, bentonite, talc,attapulgite and montmorillonite); synthetic mineral substances such as highly dispersible silicic acid, aluminium oxide and silicates; organic substances such as cellulose, starch, urea and synthetic resins; and fertilizers such as phosphates and nitrates, whereby such carrier substances can be present as powders oras granulates.

As solvents or dispersion media there essentially come into consideration: aromatics such as benzene, toluene, xylenes and alkylnaphthalenes; chlorinated aromatics and chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes and me~hylene chloride;

. ., .

~'-.
' .

1 1~6~63 aliphatic hydrocarbons such as cyclohexane and paraffins (e.g. petroleum fractions); alcohols such as butanol and glycol, as well as their ethers and esters; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; and s~y polar solvents or dispersion ~e~ia such as dimethylformamide, N-methyl--pyrrolidone and dimethyl sulphoxide, whereby such solvents preferably have flash points of at least 30C
and boiling points of at least 50C, and water. Among the solvents or dispersion media there also come into consideration so-called liquified gaseous extenders or carrier substances, these being products which are gaseous at room temperature and under normal pressure. Examples of such products are especially aerosol propellant gases such as halogenated hydrocarbons (e.g. dichlorodifluoro-methane). If a weed control composition in accordance with the invention is present in the form of a pressurized pack, then a solvent is conveniently used in addition to the propellant gas.

.

The tensides (wetting and emulsifying agents) can be non--70nic compounds such as condensation products of fatty acids, fatty alcohols or fatty-substituted phenols with ethylene oxide; fatty acid esters and ethers of sugars or polyvalent alcohols; the products which are obtained from sugars or polyvalent alcohols by condensation :. ~

-- 115~B63 with ethylene oxide; block polymers of ethylene oxide and propylene oxide; or alkyldimethylaminè oxides.

The tensides can also be anionic compounds such as soaps; fatty sulphate esters (e.g. dodecyl sodium sulphate, octadecyl sodium sulphate and cetyl sodium sulphate); alkyl sulphonates, aryl sulphonates and fatty--aromatic sulphonates, such as alkylbenzene sulphonates (e.g. calcium dodecylbenzene sulphonate and butylnaphthalene sulphonates; and more complex fatty sulphonates, for example the amide condensation products of oleic acid and N-methyltaurine and the sodium sulphonate of dioctyl succinate.

Finally, the tensides can be cationic compounds such as alkyldirnethylbenzylammonium chlorides, dialkyldimethyl-ammonium chlorides, alkyltrimethylammonium chlorides andethoxylated quaternary ammonium chlorides~

As c~ siry ~(without tenside action) there essentially come into consideration: lignin, sodium and ammonium salts of lignin sulphonic acids, sodium salts of maleic acid anhydride/diisobutylene copolymers, sodium and : ^ ammonium salts of sulphonated polycondensation products of naphthalene and formaldehyde, and sulphite lyes.

i; . , , . , ~ ~ ~ , : . .
:

As d~su~ ~, which are especially suitable as thickening agents or anti-settling agents, there can be used, for example, methylcellulose, carboxymethylcellulose, hydro~yethylcellulose, polyvinyl alcohol, alginates, caseinates and blood albumin.

Examples of suitable stabilizers are acid-binding agents (e.g. epichlorohydrin, phenyl glycidyl ether and soya epoxides~i antioxidants (e.g. gallic acid esters and butylhydroxytolue~e); W-absorbers (e.g. substitute~
benzophenones, diphenylacrylonitrile acid esters and cinnamic acid esters); and deactivators (e.g. salts of ethylenediaminotetraacetic acid and polyglycols).

The weed control compositions in accordance with the invention can contain, in addition to the compounds of formula I, synergists and other active substances (e.g. insecticides, acaricides, bactericides, other herbicides, fungicides, plant growth regulators and fertilizers). Such combination compositions are suitable for intensifying the activity or for broadening the spectrum of activity.

~ The weed control compositions in accordance with the invention generally contain between 0.1 and 99 weight percent~ preferably between 5 and 75 weight percent, of ' : ~

6~3 one or more compounds of formula I as the active substance(s). They can be present, for example, in a form which is suitable for storage and transport. In such ~ormulations ~e.g. emulsifiable concentrates) the active substance concentration is normally in the higher range, preferably between 10 and 75 weight percent, especially between 25 and 50 weight percent. These formulations can subsequently be diluted, for example, with the same or different inert substances, to give active substance concentrations which are suitable for practical use, i.e. preferably about 0.1 to 10 weight percent, especially about 1 to 5 weight percent. The active substance concentrations can, however, also be smaller or greater.

Conveniently, in the weed control compositions in accordance with the invention the solid carrier substances are present in a concentration range between 1 and 99.9~, the solvents or dispersion ~e~ia are present in a concentration range between 1 and 99.9%, the tensides are present in a concentration range between l and 20~, the ~ rs~ are present in a concentration range between 1 and 20%, the d~ s~ ~sas thickening or anti-settling agents are present in a concentration range between 0.1 and 5% and the stabilizers are present in a concentration range between 0.1 and 5%, these percentages referring to the total weight of the composition.

,, ~. ':' . ...

As mentioned above, the manufacture of the weed control compositions in accordance with the invention can be carried out in a manner known per se.

For the manufacture of pulverous preparations the active substance, i.e. at least one compound of formula I, can be mixed with solid carrier substance (e.g. by grinding together); or the solid carrier substance can be impregnated with a solution or suspension of the active substance and then the solvent or dispersion medium can be removed by evaporation, heatihg or suc]cing--off under reduced pressure. By adding tensides or d~ s~ such pulverous preparations can be made readily wettable with water, so that they can be converted ` into aqueous suspensions which are suitable, for example, - 15 as spray compositions.

The compounds of formula X can also be mixed with a tenside and a solid carrier substance to form a wettable powder which is dispersible in water, or they can be mixed with a solid pre-granulated carrier substance to form a product in the form of a granulate.

~ If desired, the compounds of formula I can be dissolved in a water-immiscible solvent such as, for exampIe, a high-boiling hydrocarbon, which conveniently contains ; .

~.

a dissolved emulsifying agent, so that the solution becomes self-emulsifying upon addition to water.
Alternatively, the active substance can be mixed with an emulsifying agent and the mixture can then be diluted with water to the desired concentration. Moreover, the active substance can be dissolved in a solvent and thereafter the solution can be mixed with an emulsifying agent. Such a mixture can likewise be diluted with water to the desired concentration. In this manner there are obtained emulsifiable concentrates or ready-for-use emulsions.

The use of the weed control compositions in accordance with the invention can be carried out according to usual application methods such as sprinkling, spraying, dusting, pouring or scattering. The metho* in accordance with the invention for the control or weeds comprises treating the locus to be protected against weeds and/or the weeds with a compound in accordance with the invention or with a weed control composition in accordance with the invention.

.: :
.

.
.` : :
:
: ~ .

The following Examples illustrate the present invention:

I. Manufacture of the active substances of formula I:

~E~

0.47 g of pyridine is added dropwise to a solution, cooled at 5C, of 1.72 g of D-2-[p-(a,a,a-trifluoro-p--tolyloxy)phenoxy]-propionyl chloride and 0.58 g of 2-iso-propylidineaminooxy-ethanol in 40 ml of benzene. The mixture is stirred at room temperature for 1 hour and subsequently evaporated to dryness under reduced pressure.
Thereafter, the residue is dissolved in diethyl ether/n-hexane (l:l) and the solution is extracted with water and dilute sodium bicarbonate solution, dried over a drying agent and finally evaporated to dryness.

The liquid residue is purified by chromatography on silica gel with acetone/n-hexane (1:7). There is obtained 2-isopropylideneaminooxy-ethyl D-2-[p-(a,~,a--trifluoro-p-tolyloxy)phenoxy]-propionate; nD = 1.5088;
[a]D = +13.9 (c = l.0~ in CHCl3).

In an analogous manner, from D-2-[p-(a,a,a-trifluoro~p-tolyloxy)phenoxy]-propionyl chloride and N-hydroxymethyl-acetamide there is obtained '': ' .

acetamidomethyl D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy~
-propionate; m.p. 103-105C; [a]D = 13.5 (c -- l 1%
in CHC13)i from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenox~-propionyl chloride and N-hydroxymethyl-chloroacetamide there is obtained chloroacetamidomethyl D-2-~p-(a,a,a-trifluoro-p--tolyloxy)phenox~-propionate; m.p. 98-99C; [a]22 19.8 (c = 0.7% in CHCl3);

from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and N-hydroxymethyl-trichloroacetamide there is obtained trichloroacetamidomethyl D-2-[p-(a,a,a-trifluoro--p-tolyloxy)phenoxy]-propionate; n20 = 1.5320; [a]D =
+14.8 (c = 0.6% in CHCl3);

from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and 2-methanesulphonamido-ethanol there is obtained 2-methanesulphonamido-ethyl D-2-[p-(a,a,a-trifluoro-p-tolyl-oxy)phenoxy]-propionate; m.p. 65-68C; [a]D = +24.6 (c = 1.1% in CHCl3);

from D-2-[p-(a, a, a-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and N-hydroxymethyl-succinimide there is obtained succinimidomethyl D-2- EP- ( a, a,a-trifluoro-p-tolyloxy)-phenoxy]-propionate; m.p. 74-76C; [a] D = +13.5 (c = 1-3% i~ CHC13);

~', ' '` '' '. ~' ~ .

.
. .
.
.,: ,.
,~ : ..

from D-2-[p-(a,a,a~trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and N-hydroxymethyl-phthalimide there is obtained phthalimidomethyl D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phen-oxy]-propionate; m.p. 99-100C; [a]D = ~4 9 (c = 0.7%
in CHC13)i from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and diethoxyphosphinylmethanol there is obtained diethoxyphosphinylmethyl D-2-[p-(,a,a-trifluoro-p-tolyl-oxy)phenoxy]-propionate; nD = 1.5008; E a]D = +27.5 (c = l.0~ in CHCl3);

from D-2-~p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and 2-diethoxyphosphinyl-ethanol there is obtained 2-diethoxyphosphinyl-ethyl D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionate; nD = 1.5001; La]D2 =~20.7 (c = 0.7% in CHCl3);

- from D-2-~p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and l-diethoxyphosphinyl-ethanol there is obtained l-diethoxyphosphinyl-ethyl D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionate; nD = 1.4963; [a]D

20 +20.3 (c = 1.3%in CHCl3);

from D-2-[p-(a,a,-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and l-diethoxyphosphinyl-n-butanol there is obtained l-diethoxyphosphinyl-n-butyl D-2-[p-(~, a, a-, -; :

1 ~ 3 -trifluoro-p-tolylo~y)phenoxy]-propionate; nD = 1.4945;
[a]D2 = +23.0 (c = 1.4% in CHC13);

from D-2-[p-(,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and a-diethoxyphosphinyl-benzyl alcohol there is obtained a-diethoxyphosphinyl-benzyl D-2-[p-(a,a,a-trifluoro--p-tolyloxy)phenoxy]-propionate; n20 = 1.5228; [a]D
+25.5 (c = 0.7% in CHC13);

from D-2-[p-(p-iodophenoxy)phenoxy]-propionyl chloride and 2-isopropylideneaminooxy-ethanol there is obtained 2-~isopropylideneaminooxy-ethyl D-2-[p-(p-iodophenoxy)phenoxy]--propionate; [a]D = +12.6 (c = 1.2% in CHC13);

from D-2-[p--(p-iodophenoxy)phenoxy]-propionyl chloride and 2-methanesulphonamido-ethanol there is obtained 2-methane-sulphonamido-ethyl D-2-[p-(p-iodophenoxy)phenoxy]-propionate;
mOpu 84-87Ct ~a]22 = +23.2 (c = 1.0% in CHC13);

, ..,, , , ~. . .. .
. . . ~

from D-2-[p-(p-iodopheno~y)phenoxy]-propionyl chloride and N-hydroxymethyl-succinimide there is obtained succinimidomethyl D-2-[p-(p-iodophenoxy)phenoxy]-propionate;
[a]D = +11.5 (c = 0.8% in CHC13);

from D-2-[p-(p-iodophenoxy)phenoxy]-propionyl chloride and diethoxyphosphinylmethanol there is obtained diethoxy-phosphinylmethyl D-2-[p-(p-iodophenoxy)phenoxy]-propionate;
[a]D = +23.7 (c = 1.7% in CHC13);

from D-2-[p-(p-iodophenoxy)phenoxy]-propionyl chloride and 2-diethoxyphosphinyl-ethanol thexe is obtained 2--diethoxyphosphinyl-ethyl D-2-[p-(p-iodophenoxy)phenoxy]-propionate; [a]D = +19.7% (c = 1.3% in CHC13);

from D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]-propionyl chloride and 2-isopropylideneaminooxy-ethanol there is obtained 2-isopropylideneaminooxy-ethyl D-2-[p-(o-chloro p-iodophenoxyjphenoxy]-propionate; [a]D = +11.7 (c =
0.9% in CHC13);

from D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]-propionyl chloride and 2-methanesulphonamido-ethanol there is obtained 2-methanesulphonamido-ethyl D-2-[p-(o-chloro-p-iodo-phenoxy)phenoxy]-propionate; [~]20 = ~19.4 (c = 008% in C~C13);

;~

15~3 from D-2-[p-(o-chloro-p-iodophenoxy)phenoxy]-propionyl chloride and diethoxyphosphinylmethanol there is obtained diethoxyphosphinylmethyl D-2-[p-(o-chloro p-iodophenoxy)-phenoxy]-propionate; ~a]D = +19.7 (c = 1.6% in CHC13);

from D-2-[p (a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and ~ibutoxyphosphinylmethanol there is obtained di~utoxyphosphinylmethyl D-2-[p-(a,a,a-trifluoro-p-tolyloxy)-phenoxy]-propionate; nD = 1.4932; [a]D = ~23.2 (c =

0.60~ in CHC13);

from D-2-[p-(a, a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and l-diphenoxyphosphinyl-ethanol there is obtained l-diphenoxyphosphinyl-ethyl D- 2-[p-( a,a,a~tri-fluoro-p-tolyloxy)phenoxy]-propionate; nD ~ 1.5449;
[a]D = +7 3 ~c = 1.1% in CHC13);

lS from D-2-[p-(a,a, a-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and l-isopropylideneaminooxy-2-propanol ~here is o~,tai.ned 1-isopropylideneaminooxy-2-propyl D 2 ~p-~a,a,a--trifluoro-p-tolyloxy)phenoxy]-propionate; nD
1.5026; [a]D = +19.0 (c.= 1.1% in CHC13);

from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyï
chloride and l-isopropylideneaminooxy-2-butanol there is obtained 1-isopropylideneaminooxy-2-butyl 3-2-~p-(a,a,a--trifluoro-p-tolyloxy)phenoxy]-propionate; nD = 1.5023, [a]D = +20.7 (c = 1.0% in CHC13);

from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl chloride and 2-isopropylideneaminooxy-1-phenyl-ethanol there is obtained 2-isopropylideneaminooxy-1-phenylethyl D-2-[p-(a, ar a-trifluoro-p-tolyloxy)phenoxy]-propionate;
[a]D2 = +19.8 tc = 0.9% in CHC13);

from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phe~oxy]-propionyl chloride and 2-(2-butylideneaminooxy)-ethanol there is obtained 2-(2-butylideneaminooxy)-ethyl D-2-[p-(a,a,a--trifluoro-p-tolyloxy)phenoxy]-propionate; nD = 1.5072;
[a]D = +13.7 (c = 1.1% in CHC13);

from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionyl chloxide and 2-(a-methylbenzylideneaminooxy)-ethanol ~o there is obtained 2-(a-methylbenzylideneaminooxy)-ethyl D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionate, nl~ - 1.5456; [a]D = +7.6 (c = 1.0% in CHC13);

: ,~

-~ tl~63 from D-2-[p-(a,a,a-tri~luoro-p-tolyloxy)phenoxy]-propionyl chloride and 2-cyclohexylideneaminooxy-ethanol there is obtained 2-cyclohexylideneaminooxy-ethyl D-2-[p-~a,a,~
-trifluoro-p-tolyloxy)phenoxy]-propionate; nD = 1.5201;
[]20 = +11.7 (c = 1.1% in CHC13).

Exam~le_2

3.0 g of D-2-[p-(a,a,a-trifluoro-p-tolyloxy)-phenoxy]-propionic acid are suspended in 10 ml of dichloromethane and 1.3 g of ethyl ~k~oxime are added at room temperature. A solution of 1.9 g of dicyclohexylcarbodiimide in 10 ml of dichloromethane is added dropwise to the suspension during 10 minutes, the temperature of the mixture thereby rlsing to40C ~.e mixture is stirred at room temperature for a ~urther 2 hours and subsequently filtered. The filtrate is evaporated to dryness under reduced pressure. There is obtained ethyl 3-/ D-2-[p-(a,a,a-trifluoro-p-tolyloxy) phenoxy]-propionoxyimino ~-butyrate; ~a]20 = ~39.8 (c =
1.0~ in CEC13)u In an analogous manner, - from D-2~[p-( a~ a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid and l,l,l-trifluoroacetone oxime there is obtained . .: :, - .
~: .

D-2- [p- ( a, a, a-trifluoro-p-tolyloxy)phenoxy]-propionic acid l,l,l-trifluoroacetone oxime ester; [a]20 = +39.50 (c = 1.0% in CHC13);

from D-2- [p- ( a, a, a-trifluoro-p-tolyloxy)phenoxy]-propiorl~c acid and l-hydroxyimino-diethyl ether there is obtained ethyl N-/ D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]--propionoxy_7-acetimidate; nD = 1.5087; [a]D = +53 (c = 0.9~ in CHC13);

from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid and n-butyl (l-hydroxyimincethyl) ether there is obtained n-butyl N- r D-2-[p-(a,a,-trifluoro-p--tolyloxy)phenoxy]-propionoxy /-acetimidate; n20 = 1.5036;
[a]D2 = +49.87 (c = 1.2~ in CHC13);

., from ~-2-[p-(ala,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid and ethyl (l-hydroxyimino-n-butyl) ether there is obtained ethyl N-~ D-2-Lp-(a,a,a-trifluoro~p-tolyloxy)-phenoxy]-propionoxy ~ -n-butyrimidatei n20 = 1.5058;
[a]D = +52.58 (c = 1.0~ in CHC13)j from D-2-[p-(a,a,a~trifluoro-p-tolyloxy)phenoxy]-propionic acid and methoxyacetone oxime there is obtained D-2-[p--(a,a,a-trifluoro-p-tolyloxy)phenoxy]--propionic acid methoxyacetone oxime ester; [a]20 = ~48.77 (c - 1.9 in CHC13);

' .,, ~
:
,:

from D-2-[p-(a,a,a-trifluoro-p--tolyloxy)phenoxy]--propionic acid and diacetone monoxime there is obtained D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid diacetone monoxime ester; [a]D = +30.7 (c = 1.0% in CHC13)i from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy~-proplonic acid and ethyl pyruvate oxime there is obtained ethyl 2- r D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionoxy-imino /-propionate; [a]D = +45.01 (c = 2.0% in CHC13);

from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy-propioniC
acid and ethyl a-methyl-acetoacetate oxime there is obtained ethyl 2-methyl-3-/ D-2-[p-(a,a,a~trifluoro-p-tolyloxy)-phenoxy]-propionoxyimino_/-butyrate; [a]20 - +41.07 (c = 0.9% in CHC13);

from D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid and ethyl levulinate oxime there is obtained ethyl

4-/ D-2-[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionoxy-imino /-n-valerate; ~]D = +37 4 (c = 1~2% in CHC13);

from D-2-[p-(o-chloro-p-trifluoromethyl--phenoxy)phenoxy]--propionic acid and 2-isopropylideneaminooxy-ethanol there is obtained 2-isopropylideneamlnooxy-ethyl D-2-[p (o--chloro-p-trifluoromethyl~phenoxy)phenoxy] propionate;
[a]20 = +12.3 (c = 0.69% in CHC13);

.

1 15~6~3 from D-2-[p-(~,a,a-tri~luoro-p-tolyloxy)phenoxy]-propionic acid and cyclopentanone oxime there is obtained D-2--[p-(a,a,a-trifluoro-p-tolyloxy)phenoxy]-propionic acid cyclopentanone oxime ester; [a]D = ~40.8 (c = 1.0%
in CHC13).

Example 3 A solution of 1.79 g of D-2-~p-(a,a,a-trifluoro--p-tolyloxy)phenoxy]-propionic acid, 1.30 g of l-diethoxy-phosphinyl-cyclohexanol and 0.06 g o 4-dimethylamino--pyridine in 20 ml of dichloromethane is treated at room temperature with 1.13 g of dicyclohexylcarbodiimide and the mixture is stirred for 24 hours. The mixture is then evaporated to dryness under reduced pressure, the residue is dissolved in diethyl ether/n-hexane (1:1) and the insoluble part of the residue is filtered off under suction. Subsequently, the filtrate is washed twice with 30 ml of 5~ acetic acid each time and three times with 30 ml of water each time, dried over a drying agent and evaporated to dryness. The liquid residue is puxified 20 by chxomatography on silica gel with dichloromethane/ ..
diethyl ether (1:1). There is obtained l-diethoxy~
phosphinyl-cyclohexyl D-2-[p-( a, a, a-trifluoro-p-tol~yloxy) phenoxy]-propionate; n20 = 1.5073.

'' ' ' ~ ' .

B~3 In an analogous manner, from D-2-[p-( a, a, a-trifluoro-p-tolyloxy)phenoxy]--propionic acid and 2-dimethoxyphosphinyl-2-propanol there is obtained 2-dimetho.~phosphinyl-2-propyl D-2-

5 - [p- ~a, a, a-trifluoro-p-tolyloxy)phenoxy]-propionate;
nD = 1.5019; [alD = +7.6 (c = 1.2~ in CHC13).

Example 4 A mixture of 1.89 g of D-2-[p-(a,a,a-trifluoro--p-tolyloxy)phenoxy]-propionic acid, 1.43 g of 3--diethoxyphosphinylpropyl bromide, 0.40 g of potassium carbonate and 50 ml of absolute acetone is heated at reflux for 15 hours~ Thereafter, the mixture is evaporated to dryness under reduced pressure and the residue is dissolved in diethyl ether. The solution is lS washed twice with 25 ml of water each time and extracted twice wit~ 25 ml of sodium bicarbonate solution each time, dried over a drying agent and evaporated to dryness.

The liquid residue is purified by chroma~ography on silica gel with dichloromethane. There is obtained 3--diethoxyphosphinyl-propyl D-2-[p-ta,a,a-trifluoro-p ~tolyloxy)phenoxy]-propionate; nD = 1.4986; [a]D
+20.52 (c = 0.9~ in CHC13)o .

In an analogous manner, from D-2-[p-(p-iodophenoxy)phenoxy]-propionic acid and 3-diethoxyphosphinylpropyl bromide there is obtained 3-diethoxyphosphinyl-propyl D-2-[p-(p-iodophenoxy)phenoxy]--propionate; [a]D = +20.4 (c = 1.2% in CHC13).

II. Formulation Examples:

Example 5 For the manufacture of an emulsifiable concentrate the following ingredients are mixed with one another:

10 Compound of formula I 500 g Mixture of condensation products of an alkylphenol and ethylene oxide and - calcium dodecylbenzenesulphonate100 g Epoxidated soya oil with an oxirane 15 oxygen content of about 6~ 25 g Butylated hydroxytoluene 10 g : The mixture is made up to 1 litre with xylene.

The thus-obtained concentrate emulsifies spontaneously in water. The resulting emulsion is suitable as a ready-for-use spray liquor.

- , . . .,:

~: ~
:
:,

6 ~ 3 Example 6 For the manufacture of an emulsifiable concentrate the following ingredients are mixed with one another:

5 Compound of formula I 250 g/l N-Methyl-2-pyrrolidone 300 g/l Emulsifier A ) 100 g/l Emulsifier B ) 25 g/l Solvent mixture of alkylbenzenes to lO00 ml ~Emulsifier A: Emulsifier consisting of 60 parts of a block polymerisate of ethylene oxide and proplyene oxide, 20 parts of the calcium salt of a branched-chain dodecylbenzenesulphonic acid and ?0 parts of a solvent mixture of isobutanol and C10~alkylbenzenes.

2)Emulsifier B: Mixture of 70 parts of the calcium salt of a branched-chain dodecylbenzenesulphonic acid and 30 parts of a solvent mixture of isobutanol and C10-alkylbenzenes .

The thus-obtained concentrate emulsifies spontaneously in water. The resulting emulsion is suitable as a ready-for-use spray liquor.

..

III. Blological Results:

Exam~le 7 The formulation of Example 6 is sprayed on the test weeds (Lolium multiflorum or Bromus inermis) in fixed dilutions with water containing 0.5 volume percent of Nonoxynol (condensation product of nonylphenol and ethylene oxide~. The spraying is carried out by means of a logarithmic spray apparatus which enables the concentration of the active substance to be halved automatically after fi~Yed ~ intervals. The ispray volume amounts to SOO l/ha. 33 days after the spraying the weeds are investigated for the effect which has occurred, i.e. there is determined the dosage at which a satisfactory control of the weeds is achieved. The results are compiled in Table I hereinafter.

~;

'' : " " ~, ' ' ' :

1 1 ~ 3 Table I

..
Dosage (g of active substance/
~ ~a) _ Active substance ofLolium Bromus formula I multiflorum inermis _ Ethyl N-/~ -2-[p-(a,a,a--trifluoro-p-tolyloxy)-phenoxy]-propionoxy /-n--butyrimidate 165 165 n-Butyl N-/ D-2-[p-(a,a,a--trifluoro-p-tolyloxy)- .
phenoxy]-propionoxy_/--acetimidate 125 220 _ . . _.~

Example 8 The active substance is tested in the formulation of Example 6. Shortly before the beginning of the test, it is diluted to the desired concentration with water containing 0.5 volume percent of Nonoxynol as the wetting agent.

The test weeds (Oryza sativa) in -the 2 leaf stage are sprayed in a greenhouse with the thus-formulated active substance. Subsequently, a 16 hours day is ,~ .

- ~........... . . ..
. ~ :
- ,~

.

1 ~ 3 simulated by means o~ mercury lamps. Three weeks arter the spraying the weeds are investigated for the effect which has occurred, i.e. the percentage necrosis is determined, with a 100% necrosis corresponding to a complete destruction of the weeds. The results are compiled in the Table II hereinafter.

Table II

Acti~e substance of Dosage % Necrosis formùla I q/ha (Oryza sativa) D-2-[p-(a,a,a-Trifluoro--p-tolyloxy)phenoxy~-propionic acid methoxy-acetone oxime ester 150 90 .; . : : . ~

Claims

The embodiments of the invention in which an exclusive pro-perty or privilege is claimed are defined as follows:

1. Compounds of the general formula I

wherein R1 signifies chlorine, bromine, iodine or trifluoromethyl, R2 signifies hydrogen,chlorine, bromine or iodine, R3 signifies hydrogen or C1-4--alkyl, R4 signifies hydrogen; C1-4-alkyl; or phenyl, optionally substituted with halogen,C1-4--alkyl and/or nitro, whereby R3 and R4 together with the carbon atom to which they are attached can also form a C5-8-cycloalkane ring which, if desired, can be substituted with 1 to 3 C1-4--alkyl groups, m, n and p signify the number 0 or 1 and R5 signifies one of the following groups (a) - (f):

-NHCO-R6 (a) -NHSO2-R7 (b) (c) (d) (e) (f) whereby in the above formulae of the groups (a) - (f) R6 signifies hydrogen; C1-6--alkyl; C1-4-haloalkyl; or phenyl, optionally substituted with halogen, C1-4-alkyl and/or nitro, R7 signifies C1-6-alkyl; or phenyl, optionally substituted with halogen, C1-4-alkyl and/or nitro, R8 and R9 stand for hydrogen or together signify a bond, tri-methylene, tetramethylene, 2--butenylene or a fused benzene ring, R10 signifies C1-6-alkyl and R11 signifies trifluoromethyl, C1 6-alkoxy, C1-6-alkoxy-C1-4-alkyl, C2-7--alkanoyl, C2-7-alkoxycarbonyl or C2-7-alkoxycarbonyl-C1-4--alkyl, or R10 and R11 together with the carbon atom to which they are attached form a cyclo-pentane ring which, if desired, can be substituted with 1 to 3 C1-4-alkyl groups and/or 1 C1-4--alkoxy group , whereby, where R1O, R11 and the carbon atom form an optionally substituted cyclopentane ring, R1 is chlorine, bromine or tri-fluoromethyl, R12 signifies hydrogen or C1-6--alkyl and R13 signifies C1-6--alkyl; or phenyl, optionally substituted with halogen, C1-4--alkyl and/or nitro, or R12 and R13 together with the carbon atom to which they are attached form a C5-7-cycloalkane ring, and R14 and R15 signify C1-6-alkyl or phenyl, and whereby, when R5 represents a group (a), (b) or (c), m signifies the number 1, n signifies the number 0 and p signifies the number 0 or 1; when R5 represents a group (d), m, n and p signify the number 0; when R5 represents a group (e), m signifies the number 0 and n and p signify the number 1;
and when R5 represents a group (f), m and p signify the number 0 or 1 and n signifies the number 1.

2. Compounds according to claim 1, wherein R1 signifies iodine or trifluoromethyl.

3. Compounds according to claim 1 wherein R2 signifies hydrogen or chlorine.

4. The D-isomers of the compounds according to any one of claims 1 to 3.

5. Succinimidomethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p--tolyloxy)phenoxy]-propionate.

6. Ethyl N-[D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-phenoxy]-propionoxy]-acetimidate.

7. n-Butyl N-[D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-phenoxy]-propionoxy]-acetimidate.

8. 2-Isopropylideneaminooxy-ethyl D-2-[p-(.alpha.,.alpha.,.alpha.--trifluoro-p-tolyloxy)phenoxy]-propionate.

9. Diethoxyphosphinylmethyl D-2-[p-(.alpha.,.alpha.,.alpha.-tri-fluoro-p-tolyloxy)phenoxy]-propionate.

10. A compound according to claim 1, selected from:

Acetamidomethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-phenoxy]-propionate, chloroacetamidomethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p--tolyloxy)phenoxy]-propionate, trichloroacetamidomethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)phenoxy]-propionate, 2-methanesulphonamido-ethyl D-2-[p-(.alpha.,.alpha.,.alpha.-tri-fluoro-p-tolyloxy)phenoxy]-propionate, phthalimidomethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p--tolyloxy)phenoxy]-propionate, 2-diethoxyphosphinyl-ethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro--p-tolyloxy)phenoxy]-propionate, 1-diethoxyphosphinyl-ethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro--p-tolyloxy)phenoxy]-propionate, 1-diethoxyphosphinyl-n-butyl D-2-[p-(.alpha.,.alpha.,.alpha.-tri-fluoro-p-tolyloxy)phenoxy]-propionate, .alpha.-diethoxyphosphinyl-benzyl D-2-[p-(.alpha.,.alpha.,.alpha.-tri-fluoro-p-tolyloxy)phenoxy]-propionate, ethyl 3-[D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-phenoxy]-propionoxyimino]-butyrate, D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)phenoxy]--propicnic acid 1,1,1-trifluoroacetone oxime ester, ethyl N-[D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-phenoxy]-propionoxy]-n-butyrimidate, D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)phenoxy]--propionic acid methoxyacetone oxime ester, D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)phenoxy]--propionic acid diacetone monoxime ester, ethyl 2-[D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-phenoxy]-propionoxyimino ]-propionate, ethyl 2-methyl-3-[D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p--tolyloxy)phenoxy]-propionoxyimino]-butyrate, ethyl 4-[D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)-phenoxy]-propionoxyimino]-n-valerate, 2-isopropylideneaminooxy-ethyl D-2-[p-(o-chloro--p-trifluoromethyl-phenoxy)phenoxy]-propionate, D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)phenoxy]--propionic acid cyclopentanone oxime ester, 1-diethoxyphosphinyl-cyclohexyl D-2-[p-(.alpha.,.alpha.,.alpha.--trifluoro-p-tolyloxy)phenoxy]-propionate, 2-dimethoxyphosphinyl-2-propyl D-2-[p-(.alpha.,.alpha.,.alpha.--trifluoro-p-tolyloxy)phenoxy]-propionate and 3-diethoxyphosphinyl-propyl D-2-[p-(.alpha.,.alpha.,.alpha.-tri-fluoro-p-tolyloxy)phenoxy]-propionate.

11. A compound according to claim 1, selected from:

2-Isopropylideneaminooxy-ethyl D-2-tp-(p-iodo-phenoxy)phenoxy]-propionate, 2-methanesulpnonamido-ethyl D-2-[p-(p-iodophenoxy)-phenoxy]-propionate, succinimidomethyl D-2-[p-(p-iodophenoxy)phenoxy]--propionate.
diethoxyphosphinylmethyl D-2-[p-(p-iodophenoxy)-phenoxy]-propionate, 2-diethoxyphosphinyl-ethyl D-2-[p-(p-iodophenoxy)-phenoxy]-propionate, 2-isopropylideneaminooxy-ethyl D-2-[p-(o-chloro-p--iodophenoxy)phenoxy]-propionate, 2-methanesulphonamido-ethyl D-2-[p-(o-chloro-p--iodophenoxy)phenoxy]-propionate, diethoxyphosphinylmethyl D-2-[p-(o-chloro-p--iodophenoxy)phenoxy]-propionate, dibutoxyphosphinylmethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro--p-tolyloxy)phenoxy]-propionate, 1-diphenoxyphosphinyl-ethyl D-2-[p-(.alpha.,.alpha.,.alpha.-trifluoro--p-tolyloxy)phenoxy]-propionate, 1-isopropylideneaminooxy-2-propyl D-2-[p-(.alpha.,.alpha.,.alpha.--trifluoro-p-tolyloxy)phenoxy]-propionate, 1-isopropylideneaminooxy-2-butyl D-2-[p-(.alpha.,.alpha.,.alpha.--trifluoro-p-tolyloxy)phenoxy]-propionate, 1-isopropylideneaminooxy-1-phenylethyl D-2-[p-(.alpha.,.alpha.,.alpha.--trifluoro-p-tolyloxy)phenoxy]-propionate, 2-(2-butylideneaminooxy)-ethyl D-2-[p-(.alpha.,.alpha.,.alpha.--trifluoro-p-tolyloxy)phenoxy]-propionate, 2-(.alpha.-methylbenzylideneaminooxy)-ethyl D-2-[p--(.alpha.,.alpha.,.alpha.-trifluoro-p-tolyloxy)phenoxy]-propionate, 2-cyclohexylideneaminooxy-ethyl D-2-[p-(.alpha.,.alpha.,.alpha.--trifluoro-p-tolyloxy)phenoxy]-propionate and 3-diethoxyphosphinyl-propyl D-2-[p-(p-iodophenoxy)-phenoxy]-propionate.

12. A process for the manufacture of compounds of the general formula I

wherein R1 signifies chlorine, bromine, iodine or trifluoromethyl, R2 signifies hydrogen, chlorine, bromine or iodine, R3 signifies hydrogen or C1-4--alkyl, R4 signifies hydrogen; C1-4--alkyl; or phenyl, optionally substituted with halogen, C1-4--alkyl and/or nitro, whereby R3 and R4 together with the carbon atom to which they are attached can also form a C5-8--cycloalkane ring which, if desired, can be substituted with 1 to 3 C1-4-alkyl groups, m, n and p signify the number 0 or 1 and R5 signifies one of the following groups (a) - (f):

-NHCO-R6 (a) -NHSO2-R7 (b) (c) (d) (e) (f) whereby in the above formulae of the groups (a) - (f) R6 signifies hydrogen; C1-6--alkyl; C1-4-haloalkyl; or phenyl, optionally substituted with halogen, C1-4-alkyl and/or nitro, R7 signifies C1-6-alkyl; or phenyl, optionally substituted with halogen, C1-4-alkyl and/or nitro, R8 and R9 stand for hydrogen or together signify a bond, tri-methylene, tetramethylene, 2--butenylene or a fused benzene ring, R10 signifies C1-6-alkyl and R11 signifies trifluoromethyl, C1-6-alkoxy, C1-6-alkoxy-C1-4--alkyl, C2-7-alkanoyl or C2-7--alkoxycarbonyl or C2_7--alkoxycarbonyl-C1-4-alkyl, or R10 and R11 together with the carbon atom to which they are attached form a cyclopentane ring which, if desired, can be substituted with l to 3 C1-4--alkyl groups and/or 1 C1-4--alkoxy group, whereby, where R10, R11 and the carbon atom form an optionally substituted cyclopentane ring, R1 is chlorine, bromine or trifluoro-methyl, R12 signifies hydrogen or C1-6-alkyl and R13 signifies C1-6-alkyl; or phenyl, optionally substituted with halogen, C1-4-alkyl and/or nitro, or R12 adn R13 together with the carbon atom to which they are attached form a C5-7-cycloalkane ring, and R14 and R15 signify Cl-6-alkyl or phenyl, and whereby, when R5 represents a group (a), (b) or (c), m signifies the number l, n signifies the number O and p signifies the number 0 or l; when R5 represents a group (d), m, n and p signify the number 0; when R5 represents a group (e), m signifies the number O and n and p signify the number 1;
and when R5 represents a group (f), m and p signify the number 0 or 1 and n signifies the number 1, which process comprises (a) reacting an acid of the formula II

wherein R1 and R2 have the significance given earlier in this claim, or a reactive derivative thereof, with a compound of the formula III

wherein R3, R4, R5, m, n and p have the significance given earlier in this claim and X signifies a leaving group, or (b) reacting a phenol of the formula IV

wherein R1 and R2 have the significance given earlier in this claim, or an alkali metal salt thereof, with a compound of the formula V

wh rein R3, R4, R5, m, n and p have the significance given earlier in this claim and Y
signifies a leaving group.

13. 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 one of the com-pounds set forth in claim 1, 2 or 3.

14. 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 one of the com-pounds set forth in claim 5, 6 or 7.

15. 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 one of the com-pounds set forth in claim 8 or 9.

16. 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 one of the com-pounds set forth in claim 10 or 11.

17. Compounds according to claim 2, wherein R2 signifies hydrogen or chlorine.

18. The D-isomers of the compounds according to claim 17.

19. 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 one of the com-pounds set forth in claim 17 or 18.