Note: Descriptions are shown in the official language in which they were submitted.
12~844~ HOE 82/F 232
The present inventionrelates to herbicidal
agents which contain a compound of the formula I
CH3
~et-O ~ O-CH-COOR (I)
in which
Het denotes
~3~ N
or x
F3C -
in which X is H or Cl, and
R denotes hydrogen, (C1-C4)-alkyl or a cation equivalent,
in combination with a compound of the formula II
Cl
- ; N ~ CH2 ~ COOR (I`L)
` S~C ~ o
in which R has the abovementioned meaning, and with the
compound of the formula III
i . ~
' ~"~
~Z~ 4~
f ~ ~III)
Cl COOH
wherein
the mixing ratio of the components of the formulae
III is within the range from 3: (3:1) to 20: (9:1).
Suitable cation e~uivalents for the radicals R
of the formulae I and II are metal cations, such as, for
example, alkali and alkaline earth metal cations or ammonium
cations which are optionally substituted by alkyl.
In formula II, R preferably denotes ethyl.
The compounds of the formula I possess a center
of asymrnetry and can therefore exist as pure enantiomers
or as mixtures of enantiomers.
Amon~st the compounds of the formula I, the
following are of particular interest for the pr~sent invention:
ethyl ~ (6-~hlorobenzthiazol-2-yloxy)-phenoxy]-~rop-
ionate (I a),
methyl a-[4-(3-chlQro-5-trifluoromethyl-pyrid-2-yloxy)~
phenoxy]-propionate (I b) and
butyl ~-[4-(5-trifluoromethyl-pyrid-2-yloxy)-phenoxy]-
propionate (I c)0
The compounds of the formula II and III are
described in "The Pesticide Manual" of the British Crop
Protection Council, 6th edition 1979, pages 28 and 1750
- 3a -
~Z~449
The compounds o the :Eormula I are particularly
suitable for combating grass-like plants, such as, Eor
example, Avena sp., Alopecurus myosuroides, Hordeum sp.,
Lolium sp. and Triticum sp.
. ,!
- 4 -
The compounds of the formula II are effective
against dicotyLedonous plants, for example Stellaria
med;a and Galium aparine; the compound of the formula III
;s particularly effective against leguminosae and other
dicotyledonous plants, such as, for example~ Polygonum
sp. and Matricaria sp.
The comb;nation of the compound of the formula II
in which R ;s ethyl tethyl 4-chloro-2-oxobenzthiazol;n-3-
ylacetate (II a)~ with the compound of the formula rII
~3,6-dichloropicolinic acid (III)) is published in Proc~
~ 13th British Weed Control ~onference, Volume 2, 517 - 524.
Surprisingly, a strik;ng synerg;stic action has
been found in attempts to comb;ne the three types of
act;ve compound ;n order to enlar~e the spectrum of
action.
The active compound combinations accord;n~ to the
;nvention can be employed to combat undes;rable species
of plants~ such as, for example, Avena sp., Alopecurus
myosuro;des, Hordeum sp.~ Lolium sp., Tr;t;cum sp.,
Stellaria med;a and Matricar;a sp~ in crops of useful
plants, part;cularly in rape.
The proport;ons by weight of the components I :
II: III can vary w;thin w;de lim;ts. They can vary from
3:~3:1) to 20:~9:1) and are particuLarly in the range
from 4:(5:1) to 8:(7:1).
The combinations according to the invent;on can
be used e;ther as tank mixtures in which the ;nd;vidual
a~tive compound components are not mixed with one another
until ;mmediately bFfore application, or as finished
~ - 5 ~ lZ~8~9
formulations. As finished mixtures they can be forrr,ula~
ted, for example, in the form of wettable powders, emul-
s;f;able concentrates, solut;ons, d;spers;ons, dust;ng
agents or ~ranules, and then contain, if appropriate, the
conventional formulation aux;liaries, such as wet~ing
agents, adhesives, emulsif;ers, dispersing agents, sol;d
or liquid inert substances, grinding aux;l;aries and
solvents.
Wettable powders are preparations which can be
un;formly dispersed in water and which can, in add;t;on
to the act;ve compound, also conta;n, as well as opt;onal
d;luents and inert substances, wetting a~ents, for
example polyoxyethylated alkylphenols, polyoxyethylated
oleylam;nes or stearylamines and alkylsulfonates or
~5 alkylphenylsulfonates, and dispersing agents~ for example
sodium lign;nsulfonate, sod;um 2,2'-d;naphthylmethane-
6,6'-disulfonate, sod;um d;butylnaphthalenesulfonate or
the sod;um salt of oleylmethyltauride.
Emulsifiable concentrates can be prepared, for
example, by d;ssolving the active compound in an organic
solvent, for example butanol, cyclohexanone, dimethyl-
formam;de, xylene, isophorone or higher-bo;l;ng aromatic
compounds, w;th the add;t;on of one or more emuls;fiers.
The following are examples of emulsif;ers wh;ch can be
Z5 used: calc;um alkylarylsul~onates, polyglycol esters of
~atty acids, alkylaryl polyglycol ethers~ fatty alcohol
polyglycol ethers, polyoxyethylated oleylam;nes or stearyl-
am;nest propylene ox;de~ethylene oxide condensat;on pro-
duc~s, alkyl polyethers, sorb;t3n esters of fatty ac;ds~
" .
~ - 6 ~ 4~
alkylaryl/propylene oxide/ethylene oxide condensat;on
products and others.
Dustin~ agents are obtained by grinding the
active compound with finely divided solid substances, for
example talc, natural clays, such as kaolin, bentonite or
pyropbillite, or diatomaceous earth.
Granules can be prepared either by atomizing a
solution of the active compound onto adsorptive granula-
ted inert material or by applying active compound con-
centrates by means of a binder, for example polyvinylalcohol, sodium polyacrylate~ methylhydroxyethylcellulose
or mineral oils, to the surface of carriers, such as sand
or kaolinite, or granulated inert material. It is also
possible to prepare suitable formulations of active com-
pounds in .he manner customary for the preparàtion offertil;zer granules - if desired as a m;xture ~ith fert;-
lizers~
The synergistic active compound mixtures, accord--
ing to the invention, of compounds of the formulae I, II
and III can be formulated in the form of conventional
preparat;ons, ;n part;cular as wettable powders, emuls;-
f;able concentrates, solut;ons~ dispersions, dust;ng
agents or granules. The total content of act;ve compound
of commercial formulat;ons is then approx. 2 to 95% by
2S weight, preferably 10 to 70% by we;ght, the relaainder up
to 100% by we;yht be;ng composed of conventional formu-
lation auxiliaries, such as adhPsives, wetting agents,
emulsifiers, dispersing agents, fillers, solvents and
carriers.
~ _ 7 _ ~2~8449
The total concentration of act;ve compound in
wettable powders var;es with;n the range from about 10
to 70X by weight, it being possible for the concentrations
of the ind;vidual components I or II and III to be bet-
~een 3 and 50% by weight, dependin~ on the ratio of theco~ponents I, II and III. The remainder up to 100% by
weight is composed of convent;onal formulat;on auxili-
aries. In the case of emulsifiable concentrates, the
total concentration of active compound is within the
range from about 10 to 70% by weight, it being possible
for the concentration of the component I to vary between
3 and 30% by weight, the concentration of the component
II to vary between 3 and 4D% by weight and that of the
component III to vary between 2 and 20% by weight, depend-
ing on the ratio of the components I~ II and III~ In thecase of granuLes, the total concentration of active com-
pound ;s about 2 to 10~ by ~le;ght. Formulat;ons in the
form of dust contain about 5 to 20% by we;ght of the
mixture of active compounds.
The ;nventîon also relates, therefore, to herb;-
c;dal agents conta;ning 2 to ~5% by we;ght, preferably
10 to 70% by we;ght, of an act;ve compound comb;nation of
compounds of the formulae I, II and III, the rema;nder
up to 100% by we;ght be;ng ~omposed of convent;onal for
mulat;on aux;l;ar;es.
For application, the concentrates mentioned are,
if appropriate, d;luted in a customary manner, for
example wettable powders, emulsifiable concentrates and
dispersions are diluted with water~ Preparations in the
,
~Z~34~
form of dust and granules and also atomizable solutions
are generally not diluted further with other inert sub-
stances before application. The required applicat;on
rate of the agents according to the invention also varies
5 with the external conditions, such as the temperature,
humidity and other factors. It can vary within uide
limits and is generally between 0.2 and ~0 kg of active
compound combinat;on per hectare, preferably between D.3
and 1.5 kg per hectare.
The invention is ;llustrated by means of the
foLlowing examples.
FORMULATION EXAMPLES
~ .
An emulsifiable Goncentrate is obtained from:
5 12.7X by ~eight of ethyl 2-t4-~6-chloro-2-benzthiazolyl-
oxy3-phenoxy)~propanoate,
16.9% by weight of ethyl 4-chloro-2-oxobenzthiazolin 3
ylace~ate,
2.5X by ~eight of 3,6-dichloropicolinic acid,
12.0% by we;ght of ethoxylated triisodecyl alcohol,
30.9~, by weight of xylene,
10.0% by weight of cyclohexanone,
9.5% by weight of fatty acid polyglycol ester and
5~5X by weight of the Ca salt of an alkylarylsuLfonic
acid.
The emulsifiable concentrate is prepared by dis-
solving the 3 active compounds in the quantities of sol-
vent indicated, with gentle heating, and then adding the
emulsifiers with stirring and, after further stirring,
_ 9 _ ~2~449
slo~lly adding the wetting agentl The resulting
substantially clear solution is filtered, and its
emuls;fy;ng quality is then checked.
Example 2
S 10.2% by ~eight of ethyl 2-(4-(6-chloro-2-benzthiazolyl-
- oxy)~phenoxy) propanoate,
16.9% by weight of ethyl 4-chloro-2-oxobenzth;azolin-3-
ylacetate,
5.0% by weight of 3,6-dichloropropionic acid,
lZ~0% by weight of ethoxylated nonylphenol,
35.0X by we;ght of xylene,
5.0% by weight of cyclohexanone,
5~0% by weight of the Ca salt of an alkylarylsulfon;c
acid,
6~X by weight of fatty acid polyglycol es~er and
4.~% by weight of an alkylaryl polyglycol ether.
The emulsifiable concentrate is prepared as
indicated under Example 1
Example 3
0 12.7% by weight of ethyl 2-~4-~6-chloro-2-benzthiazolyl-
oxy3-phenoxy)-propanoate,
13.4% by we;ght of ethyl 4-chloro-2~oxobenzthiazolin-3-
ylacetater
h.OX by we;ght of 3,6-dichloropicolinic acid,
12.D% by ueight of ethoxylated tridecyL alcoholr
5.0X by weight of N-methylpyrrol;done~
30.0% by weight of xylene,
5.U% by ~e;ght of cyclohexanone,
6rOX by weight of the Ca salt of an alkylarylsulfonic acid,
lZ~ 49
- 10 -
5.5% by weight of fatty alcohol polyglycol ether and
4 4~ by wei~ht of an alkylaryl polyglycol ether.
The emulsion concentrate is prepared as ;ndicated
under Example 1.
Example ~
A water-dispersible wettable powder ;s obtained
from:
12.7X by we;ght of ethyl 2-(4-(6-chloro-2-benzthiazolyL-
oxy)-phenoxy~-propanoate,
16~9% by weight of ethyl 4-chloro-2-oxobenzthiazolin-3-
ylacetate,
2.5X by weight of 3,6-dichloropicolinic ac;d,
12.0% by weiaht of ethoxylated tr;;sodecyl alcohol~
25.0X by weight of synthetic s;lica,
~5.0% by weight o~ basic aluminum silicate,
9.0% by weight of potassium ligninsulfonate and
~5% by weight of the sodium salt of oleylmethyltauride.
The liquid wett;ng agent ;s absorbed onto the
same quant;ty by we;ght of synthet;c siL;ca in a drum
m;xer, and the rema;n;ng const;tuents of the formulat;on
are then added and are thoroughly mixed. The mixture ;s
then ground on a pinned disk millr first at 3,000 r.p.m~
and then at 12,000 r.p.m.
B;ological Examples
In the biolog;cal examples wh;ch follow, a dis-
tinction is drawn, ;n the case of the active compound
comb;nat;ons tested, between the additive degree o~
act;on calcula~ed from the effects of the ir,dividuaL use
of ~he active compouhd components, and the experimentally
. ~ .. ......... ...
lZ~8445~
found degree of action of the active compound combina-
tions. In doing this, the known active compound com-
binations of the compounds II and III were considered as
one product ;n respect of their effects, and were com~
b;ned with the compound I.
The additive degree of action is calculated by
the formula of S.R. Colby (cf. Calculating synergistic
and antagonistic responses of herb;cide combinat;ons~
Weeds, 15, 19~7 pages 20 - 22~.
According to this formula:
~ Y ~ 100
;n ~hich
X denotes the X damage caused by herbic;de A at an
applicat;on rate of X kg per hectare,
Y denotes the % damage caused by herbicide 8 àt an
application rate of Y kg per hectare and
E denotes the expected damage caused by the herbicides A
B at an appl;cation rate of X ~ Y kg per hectare.
If the actual damage is greater than that cal-
2a culated, the effect of the combination is more than addi-
tive, i.e. a synergistic effect is present.
The test plants Hordeum vulgare, Alopecurus myo-
suroides, Avena fatua, Matricaria chamomilla, Galium
aparine and ~rassica napus were cul~ivated in pots and,
in the Z~leaf to 3~leaf stage, were sprayed with the
active compounds, each of which had been d;luted to 300
liters/hectare. The damage tdegree of action) was deter-
m;ned 3 weeks after treatment An untreated control was
.
_. .. ~ ....
- 12~ 4~
- 12 -
used in each case as a basis for reference.
As expected, it ~as found that the compo-lnds of
the formula I have no effect on dicotyledonous species
~Matricaria chamomilla~ Galium aparine or Brassica napus),
and the combinations of compounds of the formulae II and
III only have a sl;ght act;on, at fa;rly h;gh dosages, on
monocotyledonous spec;es (Hordeum vulgare, Alopecurus
myosuro;des or Avena fatua)~
In the comb;nation of the act;ve compounds of the
formulae I + II ~ III there was, surpris;ngly, an increase
in action exceeding the add;tive effect.
The degrees of action found by experiment are
l;sted in the follow;ng table. The numbers in ~) rep-
resent the values to be expected, calculated by Colby's
formula~ the observed total of the effects of the com-
pounds of the formulae II and III being taken for Y.
- 13 - 12~449
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