The invention relates to new 4-chloro-aryloxy-acetyl- or 4-chloro-aryloxy-propionyl-malonates of the general Formula I, ##STR1## a process for the preparation thereof and herbicidal compositions comprising the same. In the general Formula I PA0 R.sup.1 stands for chlorine or methyl; PA0 R.sup.2 represents hydrogen or chlorine; PA0 R.sup.3 stands for hydrogen or methyl; PA0 R.sup.4 represents C.sub.1-4 alkyl and the two R.sup.4 groups may be identical or different; and PA0 X is --N.dbd. or --CH.dbd.. The compounds of the general Formula I may be prepared by reacting a compound of the general Formula II ##STR2## with a metal derivative of a malonate of the general Formula III; ##STR3## or in the presence of an metal compound with a malonate of the general Formula III; or by reacting a compound of the general Formula IV ##STR4## with a compound of the general Formula V ##STR5## (in which Formulae R.sup.1, R.sup.2, R.sup.3, R.sup.4 and X are as stated above; Z stands for halogen and Y represents halogen, cyano or alkylcarbonyloxy). The new compounds of the general Formula I possess valuable herbicidal properties.

This invention relates to new 4-chloro-aryloxy-acetyl- and 
4-chloro-aryloxy-propionyl-malonates, a process for the preparation 
thereof, herbicidal compositions comprising the same and a method for 
combating weeds by using said compositions. 
It is known that certain aryloxy-alkane-carboxylic acid derivatives show 
herbicidal properties. Such compounds are disclosed in French Pat. No. 
1,186,520 and U.S. Pat. Nos. 2,523,228 and 2,543,397. 
According to an aspect of the present invention there are provided new 
compounds of the Formula I 
##STR6## 
wherein R.sup.1 stands for chlorine or methyl; 
R.sup.2 represents hydrogen or chlorine; 
R.sup.3 stands for hydrogen or methyl; 
R.sup.4 represents C.sub.1-4 alkyl and the two R.sup.4 groups may be 
identical or different; and 
X is --N.dbd. or --CH.dbd.. 
The new compounds of the Formula I differ from the known derivatives in the 
moiety attached to the carbonyl group. 
The new compounds of the Formula I exhibit a significantly stronger 
herbicidal effect than the known derivatives, particularly in pre-emergent 
application. The new compounds of the Formula I may be used advantageously 
in various cultures--particularly in maize--for the control of 
broad-leaved weeds--as opposed to the known derivatives the compounds of 
the present invention do not cause any damage to the cultivated plants at 
the herbicidal dose. 
A preferred compound of the Formula I is the derivative in which 
R.sup.1 is chlorine; 
R.sup.2 and R.sup.3 represent hydrogen; 
R.sup.4 is ethyl and 
X stands for --CH.dbd.. 
In a further preferred representative of the compounds of the Formula I 
R.sup.1 and R.sup.3 represent methyl; 
R.sup.2 is hydrogen, 
R.sup.4 stands for ethyl and 
X is --CH.dbd.. 
The term "C.sub.1-4 alkyl" relates to straight or branched chain alkyl 
groups having 1-4 carbon atoms (e.g. methyl, ethyl, n-propyl isopropyl, 
n-butyl). 
According to a further aspect of the present invention there are provided 
herbicidal compositions comprising as active ingredient in an amount of 
0.001-95% by weight a compound of the Formula I with suitable inert solid 
and/or liquid carriers or diluents and optionally with further auxiliary 
agents (e.g. surfactants, antifoaming, antifreezing and adhesive agents). 
The compositions of the present invention may be solid or liquid and may be 
finished in usual forms (e.g. powder mixture, dusting powder, granules, 
paste, emulsion, suspension, solution, spray, concentrate etc.). The 
compositions comprise diluents and carriers and auxiliary agents generally 
used in agriculture and plant protection. 
The solid carriers may be mineral or synthetic materials e.g. China-clay, 
siliceous earth, talc, attapulgite, diatomaceous earth, alumina, silicic 
acid and various silicates. As liquid diluent e.g. mineral oil fractions 
(e.g. gas oil, or kerosine), oils of animal or vegetable origin, aromatic, 
aliphatic or alicyclic hydrocarbons (e.g. benzene, toluene, xylene, 
cyclohexane, tetrahydro naphthalene) and derivatives thereof (e.g. 
chlorobenzene, alkyl naphthalenes, cyclohexanol, butanol) or strongly 
polar solvents (e.g. dimethyl formamide, dimethyl sulfoxide, 
N-methyl-prolidone, water) may be used. 
The surfactants (emulsifying, dispersing, wetting, antifoam or 
antiaggregating agents) may be of ionic or non-ionic character. As ionic 
surfactants the following compounds may be used: salts of saturated or 
unsaturated carboxylic acids, sulfonates of aliphatic, aromatic or 
aliphatic-aromatic hydrocarbons; sulfonates of alkyl, aryl and aralkyl 
alcohols; sulfonates of alkyl, aryl and aralkyl carboxylic acids and 
esters and ethers thereof; sulfonates of condensation products of phenols, 
cresols or naphthalene; sulfatated oils of animal or vegetable origin; 
alkyl, aryl or aralkyl phosphate esters; sulfonates and phosphates of 
polyglycol ethers of ethylene oxide formed with fatty alcohols or alkyl 
phenols. 
As non-ionic surfactants e.g. the following compounds may be used: 
condensation products of ethylene oxide formed with fatty alcohols; alkyl 
aryl polyglycol ethers; polymers of ethylene oxide and/or propylene oxide 
and derivatives thereof; alkyl cellulose. 
As antifoam agents e.g. ethylene oxide/propylene oxide condensation 
products having a low molecular weight; aliphatic alcohols; special 
silicone oils or fatty acid amides may be used. 
As adhesive or thickening agent e.g. alkaline earth metal soaps; salts of 
sulfosuccinic acid esters; or natural or synthetic macromolecular 
materials which are soluble or swellable in water may be used. 
As antifreezing agent e.g. ethylene glycol, propylene glycol or glycerol 
may be used. 
The herbicidal compositions of the present may be prepared by known methods 
of pesticidal industry by admixing at least one compound of the Formula I 
with suitable inert solid and/or liquid carriers or diluents an optionally 
with auxiliary agents. 
According to a still further aspect of the present invention there is 
provided a method for controlling weeds which comprises applying onto the 
objects to be protected--preferably onto plants, parts of plants or 
soil--an effective amount of a compound of the Formula I or a composition 
comprising the same. 
According to a still further aspect of the present invention there is 
provided a process for the preparation of compounds of the formula I which 
comprises 
(a) reacting a 4-chloro-aryloxy-alkane carboxylic acid derivative of the 
Formula II 
##STR7## 
wherein above and Y represents halogen, cyano or C.sub.1-6 
alkyl-carbonyloxy with a metal derivative of a malonate of the Formula III 
##STR8## 
or in the presence of a metal compound--preferably magnesium 
chloride--with a malonate of the Formula III; or 
(b) reacting a hydroxy aromatic compound of the Formula IV 
##STR9## 
or an alkali metal salt thereof with a malonate of the Formula V 
##STR10## 
Z represents halogen. 
According to process (a) it is preferred to use a sodium, potassium or 
magnesium derivative the malonate of the Formula III. If the malonic acid 
derivative of the general Formula III is used per se it is preferred to 
carry out the reaction in the presence of magnesium compound particularly 
magnesium chloride as metal compound. The reaction may be carried out 
preferably in an inert solvent. As solvent advantageously a hydrocarbon 
(e.g. benzene, toluene or xylene), an ether (e.g. diethyl ether, 
1,2-dimethoxy ethane, tetrahydrofuran or dioxan) an amide (e.g. dimethyl 
formamide, hexamethyl phosphoric acid triamide) a ketone (e.g. acetone or 
diethyl ketone) or a nitrile (e.g. acetonitrile) may be used. 
The malonic acid derivatives of the Formula III are reacted in the form of 
a metal salt thereof with the compound of the Formula II. The metal salts 
of the malonates may be prepared previously, e.g. by reacting a malonate 
of the Formula III with an alkali or alkaline earth metal compound. 
According to an other alternative the reaction of the compounds of the 
Formula II and III is carried out in the presence of a metal 
compound--preferably magnesium chloride. In this case the metal salt of 
the malonate of the Formula III is in situ formed in the reaction mixture. 
The reaction may be accomplished at a temperature between -10.degree. C. 
and +180.degree. C., preferably at 30.degree.-100.degree. C. The desired 
compound is separated by known methods after the removal of the 
by-products formed. 
The malonates of the Formula III and metal salts thereof and the starting 
materials of the Formula II are partly known compounds. Such compounds are 
disclosed in U.S. Pat. No. 2,223,228 and in the publications Org. Synth. 
Coll. Vol. IV, 285 and J. Org. Chem. 50, 2622 (1965). The new compounds of 
the Formula II may be prepared in an analagous manner to the process 
described in the said publications. 
According to process (b) the compounds of the Formulae IV and V are reacted 
preferably in the presence of an inert solvent or diluent. As reaction 
medium the solvents disclosed above in connection with process (a) may be 
used. It is preferred to work in the presence of an acid binding agent, 
e.g. an alkali hydroxide, alkali carbonate, alkali ethylene or alkali 
tert.butylate (preferably sodium or potassium hydroxide, carbonate, 
ethylate or tert.butylate) or any suitable organic base (e.g. triethyl 
amine). 
Further details of the present invention are to be found in the following 
Examples without limiting the scope of protection to said Examples.

EXAMPLE 1 
Preparation of diethyl-2',4'-dichloro-phenoxy-acetyl-malonate 
(a) A 50% etheral solution of 24 g of 
2',4'-dichloro-phenoxy-acetyl-chloride is added dropwise under stirring to 
a mixture of diethyl-ethoxy-magnesium malonate prepared from 17.6 g of 
diethyl malonate and 50 ml of ether. The addition of the acid chloride 
having been completed the reaction mixture is heated to boiling for an 
hour, cooled to room temperature and washed successively with 100 ml of 5% 
sulfuric acid, 100 ml of a 6% sodium bicarbonate solution and 100 ml of 
water. The etheral phase is evaporated, the excess of the malonate is 
distilled off and the residue is taken up in 100 ml of benzene. This 
mixture is subjected to chromatography on a column containing 20 g of 
silica and the column is washed with 50 ml of benzene. The united eluates 
are evaporated. Thus 31 g of the pale yellow crystalline desired compound 
are obtained, yield 85%, mp.: 110.degree.-115.degree. C. 
(b) Into a 500 ml flask equipped with a stirrer and a dropping funnel 9.52 
g of anhydrous magnesium chloride and 100 ml of anhydrous acetonitrile are 
weighed in. To the hetergeneous mixture 16.0 g of diethyl malonate are 
added. The reaction flask is placed into an ice bath and 20 ml of triethyl 
amine are added. To the solution 23.9 g of 2',4'-dichloro-phenoxy-acetyl 
chloride are added at 0.degree. C. under stirring within 15 minutes. The 
reaction mixture is stirred at 0.degree. C. for an hour and at room 
temperature for 12 hours whereupon it is cooled to 0.degree. C. and 60 ml 
of a 5M hydrochloric acid solution is added. The solution thus obtained is 
extracted three times with 100 ml of ether each, the united extracts are 
dried over magnesium sulfate and the solvent and the traces of diethyl 
malonate are removed. The residual pale yellow oil slowly solidifies on 
standing. Thus 32.7 g of the desired compound are obtained, yield 91%, 
mp.: 110.degree.-115.degree. C. 
EXAMPLE 2 
Preparation of dimethyl-2'-methyl-4'-chloro-phenoxy-acetyl-malonate 
A 50% etheral solution of 26 g of 2'-methyl-4'-chloro-phenoxy-acetyl 
bromide is added dropwise to a mixture of dimethyl-ethoxy-magnesium 
malonate prepared from 14.5 g of dimethyl malonate and 50 ml of ether. 
When the addition of the acid bromide is completed the reaction mixture is 
heated to boiling for an hour and the reaction mixture is worked up as 
described in Example 1. Thus 25 g of the desired compound are obtained in 
the form of a viscous oil which solidifies to pale yellow crystals on 
standing, yield 81%, mp.: 70.degree.-74.degree. C. 
EXAMPLE 3 
Preparation of diethyl-2-(2',4'-dichlorophenoxy)-propionyl-malonate 
A mixture of 25 g of 2-(2',4'-dichloro-phenoxy)-propionyl chloride and 30 
ml of ether is added dropwise to a 35% etheral solution of 
magnesium-diethyl malonate prepared from 17.6 g of diethyl malonate. When 
the addition of the acid chloride is completed the reaction mixture is 
heated to boiling for an hour and worked up as described in Example 1. 
Thus 29 g of the desired compound are obtained in the form of a yellow 
oil, yield 76%, n.sub.D.sup.25 =1,355. 
EXAMPLE 4 
Preparation of diethyl-2-(2'-methyl-4-chloro-phenoxy)-propionyl-malonate 
(a) Into a 200 ml round-bottomed flask equipped with a magnetic stirrer, a 
thermometer, a dropping funnel and a calcium chloride tube 100 ml of 
toluene, 10.1 g of triethyl amine and 21 g of 
2-(2'-methyl-4'-chloro-phenoxy)-propionic acid are weighed in. The 
reaction mixture is cooled under 0.degree. C. and 10.8 g of ethyl chloro 
formiate are added dropwise at such a rate that the temperature should be 
between -1.degree. C. and 0.degree. C. The thick suspension formed is 
stirred for a further period of 20 minutes, whereupon a mixture of 
diethyl-ethoxy-magnesium-malonate prepared from 17.6 g of diethyl malonate 
and 50 ml ether is added dropwise at such a rate that the temperature 
should not exceed 0.degree. C. The reaction mixture is allowed to stand at 
room temperature for 16 hours and worked up as described in Example 1. 
Thus 31 g of the desired compound are obtained in the form of a pale 
yellow oil, yield 88%, n.sub.D.sup.25 =1.348. 
(b) 25.1 g of diethyl-2-chloro-propionyl-malonate and 14.2 g of 
4-chloro-o-cresol are dissolved in 100 ml dimethyl formamide. The mixture 
is stirred at 60.degree. C. for 48 hours in the presence of 13.8 g of 
potassium carbonate. The reaction mixture is filtered and the filtrate is 
evaporated. The residue is dissolved in 100 ml of benzene and washed 
successively with 100 ml of a saturated aqueous sodium bicarbonate 
solution and 100 ml of water. The benzene phase is evaporated to yield 28 
g of the desired compound, yield 80%. 
(c) A mixture of 25.1 g of diethyl-2-chloro-propionyl-malonate, 16.5 g of 
sodium 4-chloro-2-methyl-phenolate and 100 ml of dimethyl formamide is 
stirred at 60.degree. C. for 48 hours. The reaction mixture is filtered 
and the filtrate is evaporated. The residue is dissolved in 100 ml of 
benzene and washed succesively with 100 ml of a saturated aqueous sodium 
bicarbonate solution and 100 ml of water. The benzene layer is evaporated 
to give 28.7 g of the desired compound, yield 82%. 
EXAMPLE 5 
Preparation of diethyl-2-(2',4',5'-trichloro-phenoxy)-propionyl-malonate 
One proceeds in an analogous manner to Example 4 except that 27 g of 
2-(2',4',5'-trichloro-phenoxy)-propionic acid are reacted first with 12 g 
of pivaloyl chloride and thereafter with diethyl-ethoxy-magnesium malonate 
prepared from 17.6 g of diethyl malonate. The reaction mixture is worked 
up. Thus 37 g of the desired compound are obtained in the form of pale 
yellow crystals, yield 91%, mp.: 62.degree.-66.degree. C. 
EXAMPLE 6 
Preparation of 
dimethyl-2-(3',5',6'-trichloro-2-pyridyloxy)-propionyl-malonate 
A solution prepared from 4.6 g of sodium, 26 g of dimethyl malonate and 60 
ml of ether is added dropwise to a mixture of 28 g of 
2-(2',4',5'-trichloro-2-pyridyloxy)-propionyl chloride and 50 ml of ether. 
The reaction mixture is heated to boiling for 2 hours and worked up as 
described in Example 1. Thus 26 g of the desired compound are obtained in 
the form of pale yellow crystals, yield 71%, mp.: 53.degree.-57.degree. C. 
EXAMPLE 7 
Preparation of methyl-propyl-2-(2',4',5'-trichloro-phenoxy)-propionyl 
malonate 
27 g of 2-(2',4',5'-trichloro-phenoxy)-propionic acid are reacted in an 
analogous manner to Example 4(a) at first with 12 g of pivaloyl chloride 
and thereafter with methyl-propyl-ethoxy-magnesium malonate prepared from 
17.6 g of methyl-propyl malonate. The reaction mixture is worked up. Thus 
37 g of the desired compound are obtained in the form of a pale yellow 
crystals, yield 91%, mp.: 60.degree.-64.degree. C. 
PREATION OF HERBICIDAL COMPOSITIONS 
EXAMPLE 8 
Granules having an active ingredient content of 0.01% 
2.3 g of technical grade compound No. 1 (purity 89%) are dissolved in 97.7 
g of methylene chloride to yield a solution of a concentration of 2% by 
weight. An acidic pearl siliceous earth carrier prepared from 4000 g of 
diatomaceous earth are placed into a Loedige 20 type turbine stirrer; the 
average particle size of the carrier is between 0.5 and 2 mm. 20 g of the 
active ingredient premix (2% mm/m solution) are sprayed onto the 
granulated carrier throught Tee-Jet 10080 nozzles at a rate of 5 
g/minutes, whereby the granules are stirred in the Loedige type stirrer 
with a velocity of 50 r.p.m. The sorption type granules are packed. 
EXAMPLE 9 
Sprayable powder having an active ingredient of 95% 
240 g of compound No. 2 (purity 97%; previously powdered in a mill equipped 
with a rotating blade) are admixed with 2.5 g of Cab-O-Sil M5 amorphous 
silica; carrier) and 7.5 g of type 1494 dispersing agent (sodium salt of 
the condensation product of sulfonated cresole and formaldehyde) in a 
mortar. The powdered mixture is ground in a turbine mill (Alpine LMRS-80) 
under an injected air pressure of 5 bar and a grinding air pressure of 4.5 
bar at a feeding rate of 250 g/h. Although the sprayable powder thus 
obtained contains no separate wetting agent it is readily wettable, and 
has a maximal particle size of 20 .mu.m. In a spray of a concentration of 
10 g/l the floatability at 30.degree. C. after 30 minutes is as follows: 
84% in CI standard D water; and 
91% in CI standard A water. 
EXAMPLE 10 
Emulsifiable concentrate with an active ingredient content of 24% 
40 g of Tween 85 (ethoxylated sorbitane trioleate) and 30 g of Sapogenat 
T-180 (ethoxylated tributyl phenol) emulsifiers and 250 g of technical 
grade compound No. 4 (purity: 96%) are dissolved in 400 g of cyclohexanone 
at 40.degree.-45.degree. C. under stirring. When all the components are 
dissolved the solution of the active ingredient (temperature 
40.degree.-45.degree. C.) is poured into a mixture of 200 g of 
ion-exchanged water and 70 g of ethylene glycol under vigorous stirring 
whereupon the mixture is cooled to 15.degree.-20.degree. C. Before the 
termination of the stirring period 10 g of Silicon S RE antifoam agent (a 
30% emulsion of dimethyl silicone oil) are added to the emulsion and five 
minutes later the stirring is stopped. 
EXAMPLE 11 
Biological application of the composition 
Grass seeds and seeds of cultivated plants are sown into sand of the river 
Danube in plastic boxes (size 10.times.10.times.10 cm) and compositions 
prepared from the emulsifiable concentrates of the test compounds are 
sprayed onto the surface of the sand (pre-emergent treatment) and three 
weeks after sowing (post-emergent treatment). The plastic boxes are 
watered at a rate required for normal plant growth and are kept in a glass 
house. The results of the treatment are evaluated after a test period of 
four weeks and evaluated with the aid of a scale from 0 to 10, wherein 0=n 
symptoms and 10=completely destroyed infected plants (100%). 
As reference compounds two commercially available herbicides are used, 
namely mecocrop (chemical name: 2-84'-chloro-2'-methyl-phenoxy)-propionil 
acid) and 2,4-D (chemical name: 2,4-dichloro-phenoxy-acetic acid). 
The results are summarized in Table I. It appears from the said data that 
the activity of the compounds of the present invention--as the average 
activity against grassy weeds--is superior to that of the reference 
compounds, particularly in pre-emergent application. 
The tolerance of a number of cultivated plants against the compositions of 
the present invention has been determined by means of the methods of 
treatment disclosed in this Example. It has been found that dicotyledonous 
cultivated plants tolerate well all the compositions of the present 
invention and in the herbicidal dose none of the invention compounds cause 
any phytotoxical symptoms. 
TABLE I 
__________________________________________________________________________ 
Herbicidal activity of the compounds of the general Formula I against 
various weeds in several 
cultivated plant cultures in pre-emergent and post-emergent treatment. 
Dose Autumn 
Test compound 
kg active 
AM CH SI AB GA maize whest sorghum 
Example No. 
ingredient/ha 
pre 
post 
pre 
post 
pre 
post 
pre 
post 
pre 
post 
pre 
post 
pre 
post 
pre 
post 
__________________________________________________________________________ 
1 0.5 8 8 8 8 8 8 6 5 4 6 0 1 0 0 0 0 
1.5 10 10 10 10 10 10 9 10 8 8 0 1 2 0 1 1 
2 0.5 8 8 8 8 8 8 8 6 4 6 0 1 0 0 0 0 
1.5 10 10 10 10 10 10 10 10 9 8 0 2 0 0 0 0 
3 0.5 8 8 8 8 7 7 7 8 7 7 0 1 0 0 0 0 
1.5 10 10 10 10 10 10 10 10 10 10 0 2 0 0 0 0 
4 0.5 8 8 8 8 8 8 8 8 8 8 0 1 0 0 0 0 
1.5 10 10 10 10 10 10 10 10 10 10 0 2 0 0 0 0 
5 0.5 6 6 7 7 10 10 9 8 4 4 0 1 0 1 0 1 
1.5 9 9 9 9 10 10 10 10 9 9 0 2 1 2 1 1 
6 0.5 6 6 6 6 7 8 8 8 8 8 0 1 0 1 0 1 
1.5 9 9 9 9 10 10 10 10 10 10 0 2 1 2 1 1 
7 0.5 7 6 6 7 9 10 10 9 5 4 0 1 0 1 0 1 
1.5 10 9 8 9 10 10 10 10 9 10 0 2 1 2 1 1 
MCPP 0.5 2 3 2 3 5 6 2 5 4 6 3 3 0 0 0 0 
1.5 4 8 4 8 9 10 4 8 6 8 6 6 1 0 2 0 
2,4-D 0.5 1 3 2 3 5 6 2 5 2 2 2 1 0 0 0 0 
1.5 4 8 5 9 6 10 4 8 3 3 3 2 1 0 2 0 
__________________________________________________________________________ 
AM = Amaranthus retroflexus, CH = Chenopodium album, SI = Sinapis 
arvensis, AB = Ambrosia elatior, GA = Galium aparine