Note: Descriptions are shown in the official language in which they were submitted.
- 2 - HOE 81/~ 195
The present invention relates to herbicides
chzracterized by a content of
a compound of the formula
5}~3C \ ~O ~ O
/ P ~ C~2 ~ C}12 - CH - C \ ~I)
RO NH~ X
wherein R is hydrogen, NH4, Na, K or 1/2 Ca and X is
~OH or -NH CH(CH3~-CONH-CH(CH3)-COOH,
in combination
with a compound of formula Il
R ~ ~ O- ~ ~O-C~I-COOR1 (II)
wherein ~ is chlorine or bromlne,
X is oxygen or sulfur,
R1 i5 hydrogen, (C1-C4)alkyl or a cation
equivalent of an inorganic or organic base,
or with a compound of formula III
~3C~ O ~ -O-CH-C (III)
R 2
"~
wherein
R1 is hydrogen or halog~n,
R2 is hydroxy, (C1-C6)alkoxy or isopropyloximoxy
or the group -OKat, Kat bei~g the cation of an
inGrganic or organic base,
3~
3 -HOE 81iF 195
or with a compound of formula IV
3C- ~ ~- ~ ~O~C~I_~ ~(I~)
wherein
R is hydroxy, (C~ C6)alkoxy or the group -OKatJ Kat
being the cation of an inorganic or organic base,
or with a compound of formula V
. . ~ C ~ 2 5
~ ~ 3 7(n) (V)
CH3-fH-CH2 .
SC2H5
or with a cornpound of formula VI
C~3
Rl- ~ -O ~\ ~ -O-CH-CH-CII-C \(VJ)
~2
wherein
R1 is halogen or trifluoromethyl 9
R2 is hydroxy, (C1-C~)-alkoxy or the group -OKat,
wherein Kat is the cation of an inorganic or organic
base,
or with a compound of formula VII
532
N ~ O _ ~ ~ O-CH-C (VII)
wherein A is -CH- or -N-,
X is a halogen,
n is 0, l or 2,
Rl is hydrogen or (Cl-C4)alkyl and
R2 is hydroxy, alkoxy or the group -OKat, wherein Kat
is the eation of an inorganic or organic base,
the components oE formulae I and II to VII being present in
synergistic proportions.
The eompound of formula I wherein R is hydrogen and X
:is ~OH is also known under the name phosphinotrieine.
Partieularly preferred is the compound of formula I
wherein R is NH4 and X is -OH (= compound Ia, the ammonium salt of
phc)sphinotricine). It is disclosed in German Offenlegungssehrif-t
2,7:L7,4~0 and may be used as a raeemie eompound as well as an
opt:ically aetive L-form. Preference is furtner given to eompounds
oE formula :[ wherein X is -NH-CH(CH3)-CONH-CH(CH3)-COOH, whieh
are clisclosed, for example in German Offenleyungsschrift 2,848,224.
The eompounds of formula II are disclosed, for example,
in German Offenlegungsschrift 2,640,730. Particularly preferred
are eompounds of formula II wherein X is O, R is Cl and Rl is
-C2H5 (= compound IIa) as well as compounds of formula II wherein
X is S, R is Cl and Rl is -C2H5 (= compound lIb).
From among compounds of formula III those are preferred
. A
5;3~
wherein Rl is H and R2 is -OCH3 (= compound IIIa), which a.re
dlsclosed, for example, in Zschr. krkh. Pfl. sch. SH VIII (].977),
page 429, as well as the correspond.ing isopropyloxime ester, R
in formula III being hydrogen and R2 being -0-N=C(CH3)2
(= compound IIIb),
-4a-
,~
i3;~:
- 5 - . HOE 81/F 195
which is described, by way of example, in European Patent
Specification 2246.
From among compounds of formula IV those are preferred
wherein R is O~(CH2)3-CH3 (= compound IVa9 common
name: fluazifopbutyl). It is described, for example, in
Proc. 1980 British Crop Protection Conf., page 29.
The compound V is.described, for example, in EWRS-
Symposium, Mainz, page 317.
From among the compounds of formula VI those are pre-
ferred wherein R1 i.s -CF3 and R2 is -OC2H5 (= com-
pound VIa, common name: difenopentene). It is described,
for example, in Japanese laid-open patent application
7g/154723.
The compounds of formula VII are known, for example,
from German Offenlegungsschrift 3, 004, 770 .
The compounds of formula I are active in combatting
annual and perennial weeds of many botanical families in
doses of from 0.5 to 1.5 kg/ha of active substance, pre~
ferably~ ln perennial T,Jeeds this action may last partially
f`or a considerable period of time. In perennial Gramineae,
the action i5 not always satisfactory. There is obtained,
certainly, a relatively rapid short-time "burning effect~'
on the green plant parts (stems and leaves), the action
frequently does not last for a very long time, however.
On the other hand it is known from compounds of formu-
la II to VII that they have a specific action against
annual and perennial weed grasses. This biological action
is relatively uniformous for said substances, although
they have a different chemical structure~ They are more-
over advantageous in that they can be used for combatting
selectively weed grasses in dicotyledonous crops such as
sugar beets, rape, beans, soybeans and cotton. They may
be highly efficient in the treatment of emerged weed
grasses and they are likewise very efficient in many
cases in soil treatment, that means, in preventive appli-
cation against plants germinating from seed.sO Depending on
the soil humidity or on the positiuon of the seeds, their
i3~
6 - HOE 81/F 195
action may a~so be unsatisfactory. They arc more or less
inefficient for combatting spacious sprout and root
systems in the soil. The doses required depend on the
preparation used. For example, for combatting couch-
grass (Agropyron repens) compound IIb is used in dosesof from 0.72 to 1.0 kg/ha and compound IIIb is used in
doses of from 1.44 to 2.16 kg/ha, while compound IIa has
to be applied in doses of far more than 2 kg/ha. To
combat effectively Lolium species or Avena fatua 9 com-
pound IIb has to be used in doses of from 0.5 to 0.75
kg/ha, while compound IIa, when applied i~ doses of from
0.2 to 0.3 kg/ha, is particularly effective in combatting
Digitaria sang_inalis or Sorghum halepense. Similar
differences also apply to substances of formuale IV to VII.
It has now been found that combinations of compounds
of formula I with compounds of formulae II to VII are
disti.nguished by surprising synergistic effects, especial-
ly in combatting perennial weed grasses, in particular
Grarnineae. For example J they-may be used ~dvantageously
in cornbatting said weed grasses in open non-agricultural
sites, on stubble-fields 9 in forests, in sites provided
ror permanent crop plantations or under similar con-
ditions.
In non-agricultural sites or on .stubble~fields, the
compounds according to the invention are used, for example,
for eombatting Agropyron rep_ns or Sorghum hal pense; in
sites provided for permanent crop plantations, they are
suitable for combatting the following Gramineae species:
Agrostis, Alopecurus, Bromus, Dactylis, Festuca 7 olium
or Poa 9 and, under tropical conditions, in particular
Imperata eylindrica. In forests they are active, for
example, against the species Deschampsia flexuosa,
Deschampsia eaespitosa Holcus lanatus, Holcus mollis, -~l
~ _ . . _ .
Calamagrostis epigeios or the genus Carex brizoides of
the family Cyperaceae.
The mixing ratio of components I to VII to com-
ponent II in the synergistic combinations according to
- 7 - HOE 81/F 195
the invention may ~ary w;thin wide limits. For example,
it ranges generally from 1:0.1 to 1:5, preferably ~rom
1:0.2 to 1:2.
The combinatlons according to the invention of
compounds of ~ormula I with compounds of formulae II to
VII can be applied either in the for~ of tank mixtures,
~here ~he active ingredients prepared individually are
mixed iMmediately before their application, or in the
form of ready-for-use formulations. In thi~ latter case,
; 10 they are rormulated as wettable powders, emulsifiable
concentrates, solutions, dispersions~ dusting agents, or
granules, and may contain the usual formulation auxilia-
rles ~uch as wetting agents, adhesives, emulsif~ers)
dispersing agents, solid or liquid inert substances and
grinding auxiliaries or solvents.
Wettable powders are ~ormulat.ions which are uni-
formly dispersible in water and which, in addition to
the active compound and a diluent or inert materi.al,
also contain wetting agents, for example, polyoxethylated
alkylphenols, polyoxethylated oleylamines or stearyl-
amines, alkylsulfonates or alkylphenylsulfonates and
disper~ing agents, for example sodium ligninsulfonate,
~odium 2,2'-dinaphthylmethane-6 7 6'-disulfonate, sodium
dibutylnaphthalen0-sulfonate or the sodium salt of
oleoyl-methyl-taurine.
; Emulsifiable concentrates are obtained by dis-
~olving the active compound in an organic solvent~ for
example, butanol, cyclohexanone, dimethylformamide,
xylene~isophorone or even higher boiling aromztics 7
and adding one or several emulsifiers. Suitable emul~
sifiers are, for example: calcium salts of alkylaryl-
sulfonic acid, fatty acid polyglycol esters, alkylaryl~
polyglycol ethers, fatty alcohol polyglycol ethers,
polyoxethylated oleyl or stearylamines, condensation
products based on propylene oxide and ethylene oxide,
alkylpolyethers, sorbitan~fatty.acid esters, conden-
~a~ion products based on alkylaryl, propylene oxide and
153~
- 8 - E F, 81/F 195
e~hylene oxide and the like.
Dus~ing agents are obtained by grinding the active
compound with firaly divided solids, for example talc,
natural clays, such as kaolin, bentonite, pyrophilite
or diatomaceous earth~
Granules can be manufactured either by spraying a
solution o~ the active compound onto absorbent 9 granular
inert material or by applyir.g active compound concen-
trates by means of adhesives, for example polyvinyl
alcohol, sodium polyacrylate, methylhydroxyethyl
cellulose or even mineral oils 9 onto the surface of
carriers, such as sand, ~aolinites or granular inert
rnaterial. Suitable for~ulations can also be manufactured
by the customary methods of manufacture of fertilizer
granules, if desired, in admixture with fertilizers.
The synergistic mixtures of active substances
accordin~ to the invention of compounds of formula I
with compounds of formulae II to VII may be present in
the form of the usual formulations, in particular as
wettable powders, emulsifiable concentrations, solutions,
dispersior.s, dusting ag2nts or granules. The total con--
tent of act.ve substances of the marketable formulations
is from about 2 to 95 weight %, preferably from about
5 to 80 weight %, the remainder consisting of the usual
formulation auxiliaries such as adhesives, wetting
agent~, emulsifiers, dispersing a~ents, fillers, sol~ents
and carniers.
In wsttable powders~ the total concentration of
active compounds varies, for example, between about
10 and 80 ~, the remainder consisting of the above-
mentioned 40rmulation additives. In the case of emulsi-
fiable concentrates, the total concentration of the
active compounds is ~bout 10 % to 70 ~. Sprayable solu-
tiOIlS contain about 2 ~ 20 % of active compounds. In the
case of granules, the total content of active compounds
is about 2 to 10 weight % and dust formulation3 usually
contain ~ro~ 5 to 20 weight ~ of active substances.
353:2
9 - H~E 81~F 195
If necessary or desired the commercial concentrate3
may bc diluted prior to application in the u~ual manner,
for example by means of water in the case of wettable pow-
ders 9 emulsifiable concentrates and dispcrsions. Dusts,
granules and sprayable solutions are generally ready for
use without further dilution. The amount of active ingre-
dient necessary for obtaining the desired result depends
on external conditions such as temperature, humidity and
the like. It may vary within wi~e limits and is generally
in the range from 0.1 to 10.0 kg/ha, preferably of from
0.3 to 5 kg/ha.
The following examples illustrate the invention:
A. Formulation Examples
Example 1
A wettable powder easily dispersi~le in water is
obtained by mixing thoroughly in a drum miY.er
300 weight parts of compound Ia,
100 weight parts of compound IIb,
350 weight parts of synthetic si'ici.c acid 9
~0 weight parts of calcium ligninesulfonate!
50 weight parts of polyarylsulfonate (Na-salt),
50 weight parts of the ~odium salt of o3.eoy:Lmetllyl-
tauri.c acid,
40 weight parts of polyYinyl alcohol,
30 weight parts of basic aluminum silicate (kaolinite)
and ~ub~equently crushing the result.ing mixture in a disk
attr~tion mill at 3,000 rpm. The ground material is mixed
anew ~nd ground to fine particles at 12,000 rpm.
Example 2
A wettable powder easily dispersible in water is
obtained by mixing thoroughly i.n a drum mixer
l~oo weight parts of compound Ia 9
100 weight parts of compound IIa,
300 weight parts of synthetic silicic ac.d,
70 weight part~ of potassium lignosulfonate,
50 wei.ght parts of polyacrylsulfo!late (Na-salt),
40 weight parts of the sodium salt of oleoylmeth~l
~8853~
- 10 ~ - HOE_81/F 195
tauric acid and
40 weight par~s of polyvinyl alcchol
and grinding the resulting mixture in the manner described
in Example 1 at 3,000 rpm and at 12,000 rpm subsequently.
Examples 3 to 5
Wettable powders of combinations of active substances
according to the invention may alternatively be obtained
by melting the compounds IIa and IIb, respectively 9 and by
absorbing the melt obtained in a rapid mixer in l.iquid form
on finely divided silicic acid to obtain a powder con-
centrate, which is subsequently ground in a cross~beater
mill to obtain a high fineness and homogeneity.
The resulting powder concentrate is subsequently
mixed with the compound Ia as well as with dispersing
agents and wetting agents selected from the group con~
sisting of sodium dinaphthylmethanedisulfonate, sodium
lignosulfonate, sodium 2,2-dinaphthylmethane 6,6l-di
sulfonate, sodium dibutylnaphthalenesulfona~e or sodîum
oleoylmethyltaurate. The compounds prepared according
to this method in Examples 3 to 5 have the f'ollowing
compositions:
Formulation component Composition (in weight parts)
Example 3 _Rxample ll Example 5
Compound I 40 40 45
25 Compound IIa 10 20 ~
Compound IIb -- __ 15
Silicic acid 38 20 28
Sodium oleoyl-N-
methyltauride 2 2 2
30 Sodium dinaphthyl-
methanesulfonate 10 8 ~0
B. Biological Examples
The followlng biological examples differenciate
between the additive activity calculated fro~l the indi-
vidual activity of the components of active subst~ncewhen applied alone and between the experimentally prove~
degree of activi$y of the combinations of active substance
353~
~ HOE 81/F 195
The additive degree of activity is calculated by the
formula of S.R~ Colby ~cf. Calculating ~ynergistic and
antagonistic responses of herbicide combinations, Weeds,
15, 1967, pages 20-22).
This formula is as follows:
X Y
E = X + Y - lOO
X denoting the damage in % by herbicide A in the case of
x kg/ha of quantity applied,
Y denoting the damage in % by herbicide B in the case of
y kg/ha of quantity applied,
E denoting the expected damage by the herbicides A~B in
the case o~ x+y kg/ha o~ quantity applied.
The activity of the combination of active substances
is greater than the additive activity~ if the actual
damage i9 greater than the damage calculated, that means,
a synergistic effect is observed. This is demonstrated
in the following Examples I to III, the right column and
the next-to~right column of Tables I to III indicating
the result of the combination treatment and, in brackets9
the additive activity calculated by the above formula.
~xam~le I
A field test is conducted, wherein the compourlds Ia,
IIa, IIb, IIIa, IIIb, IVA and VIa present as marketable
rormulations and in formulated combinations of Ia*IIa,
Ia~IIb, Ia-~IIIa, Ia~IIIb, Ia~IVa, Ia+V and Ia-~VIa 9
respectively, are sprayed onto an area of well de~eloped
Johnson gras~ ~Sorghurn halepense) individually in
separate tests in the form of aqueous spray liquors in
the quantities of active substance indicated in Table I
(per unit o~ area) and at the mixing ratios indicated.
The activity is evaluated 3 and 8 weeks after the treat-
ment. It is found that nei.ther compound Ia nor the other
active substances tested, when applied alone, have a
satisfactory action on the green plant parts at the dose~
used in eaeh case, and vn the further growth.
When applying the combinations according to the in~
3~
- 12 HOE 81/F 195
Yention of compou-sd Ia and the individual weed grass
herbicides, the leaves and stem.s have been destroyed
completely after 3 weeks and the permanent acti.on,
measured by the action on a second growth, is in all
tests somewhat higher than 85 % and, consequently,
higher than the values to be calculated by the formula
of Colby. Hence, a synergistic effect is obvious. The
results are sur.1marized in the following Table I:
Table I
Test on Sorghum ha _pense
Treatment with Dose of Activity (% of damage)
active substance active substance on Sorghum halepense
_ _ ~ __ __ __~ after weeks
Comp~und Ia 0.5 75 50
Compound IIa 0.12 60 50
Compound IIb 0. 6 55 20
Compound IIIa 0. 5 65 45
Compound IIIb 0. 5 70 60
Compound IVa 0. 5 75 55
Compound V 0.2 70 60
Compout1d VIa 0. 5 53 40
Compounds lalIIa 0.5 ~ 0.12 100 (90) 90 (75)
Compounds Ia~IIb 0O5 ~ 0.6 100 (89) 88 (60)
Compounds Ia-~IIIa 0.5 -~ 0.5 l00 (91) 90 (72)
Compound.s Ia~IIIb 0.5 t 0.5 100 (9~) 93 (80)
Compounds Ia-~IVa 0.5 -~ 0.5 100 (94) 90 (77)
Compounds Ia~V 0.5 + 0.2 100 (92) 95 (80)
Compounds Ia~VIa 0.5 ~ 0.5 l 00 (87) 85 (70)
~ Action on a second growth
Example II
In a test conducted on the species of weeds
Deschampsia flexuosal Calamagrostis epigeios and Carex
. . .
brizoides ir. a forest, the compounds Ia and IIb present
as market.able formlllations are sprayed onto the weed area
i.ndivi.dually and in tne form of ~he combination Ia+IIb,
respectively in the form of aqueous spray liquors in the
3~
- 13 - EIOE 81~F 195
quantities of active substances indicated in Table II (per
unit of area) and at the mixing ratios indic~ted. The
action ls evaluated 2~7 and 50 weeks after ~he treatment.
It is observed that the activit~ of the combination
according to the invention after ~ and 7 weeks on 2 of
three plant species is distinctly better than the activity
to be expected by the formula of Colby. The activity of
the comblnation according to the invention, 50 months
later, on all of the three plant species, two of which
belonging to the botanical family Gramineae and one be
longing to the botanical family Cyperaceae, is likewise
distinctly better than that reached upon application of
the individual active substances. The cGmbination is
hence dis~inguished by a distinct synergistic effect and
by a decisively improved permanent action. The results
are summarized in the following Table II:
~q
~ u~
~ Q)
L~ a
C~ ~ C ~_
-- a) c) oo o o o
.~ ~ L~
~_
~ ~ ~_
00 ~ ~o o o o
X C~
~ a) a) _,
o - a~ s~ _____
5~ ~ ~ ~~ C~
v ~ a~ o~
_,
_ _
_~
~ oo o o o
o o ~_
__
O _~
bO ~ a) a~
e ~ . _ ~-
O co `~O
U ~ ~ ~ C~
-- _
o * _~
o o In o u~
~ ~ L~ ~ a
_~~rl _~
:~,Q. td _ ~__
~ e ~ ~ o ~0 co O
d O o~ o
X __
~q a) ~ ;
c~ a) ~
~ 1 ~_
~ ~_
t~
a
r~
C~
~'~ a) ~ ~r
t~ o ~ O ~ 5
a)tH C .. ~
~O ~d ~ ~~ ~ 3
O ~ O
a) tn s~
t/~
tD O
1:~ t~
_ . . . - - O
r~ tD C)
.,1 t~ ~ tl~
H t~
tn~ tt~ H
~1
a) ,2t,~ t~ H(d
H HH S~
~ 5 O
H !::~ t/~'~
1~ S~ ~
O~; O ~ 3 ~ O
a) ~ ~ o o o ~1
,1
t/~a) ~ ~ o
td tD ~ C) O O O eq
~, E~ d t) t~
15 ~ HOE 81/F 195
Example III
. _
In this test, the compounds Ia, IIa 9 IIb and IIIa
each present in marketable formulations are sprayed in-
dividually in separate tests and the combinations Ia+IIa,
Ia+IIb and Ia+IIIa likewise present in marketable formu~
lations are likewise sprayed onto an area of the well
developed forest weed C amagrostis from aqueous
spray liquors in the quantities of active substance in-
dicated in Table III (per unit of area) or at the mixing
ratios indicated. The activity is evaluated after 4 weeks.
It is observed that the combinations according to the
invention have a far higher activity on the green plant
parts (leaves and stems) than the individual components
applied separateIy and that this activity is distinctly
higher than that calculated by the formula of Colby. The
combinations according to the invention are, consequent~
ly, distinguished by a clear synergistic effect. The
results are summarized in the following Table III:
Table III
Test conducted on Calama rostis in the ~orest
Treatment with Dose of active Activity (% of damage)
active substance substance (kg/ha) on Calamagrostis
~ _ _ __ after ~ weelcs
Compound Ia 0.5 60
25 Compound IIIa 0.75 7o
Compound IIa 0.75 50
Compound IIb 0.75 50
Compound Ia~IIIa 0.5 ~ 0.75100 (88)
Compounds Ia-~IIa 0.5 + 0.75 90 (80)
Compounds Ia~IIb 0.5 + 0.75 95 (80)
