Note: Descriptions are shown in the official language in which they were submitted.
7~6~81l
- 1
Case 5-12951/-
Synergistic composition and method of selectively
controlling weeds~ especially in cereals
The present invention relates to a synergistic
composition comprising a combination of herbioides and which
is most suitable for selectively controlling weeds in
cereals. The invention also relates to a method of
controlling weeds which comprises the use of the novel
composition, especially in cereals.
The most requently encountered and most important
- weeds at the presen~ ti~e in cereals are species of the
genera Sinapis (mustard) and ChrysenthemLm(corn marigold),
and certain Avena species (wild oats).
Excellent postemergence selectiYe herbicideY against
monocot weeds are 4-~3' ,5'-dichloropyridyl-2'-oxy)-a-
phenoxypropionic acid propargyl esters of the formula I
~Cl ~
Cl~ 0~ O-c~-co Z C~2
wherein Z is o~yge~ or sulfur.
The two co~pounds offormula~ viz. 4-(3',5'-dichloro-
pyridyl-2~-oxy~--phenoxypropionic acid propargyl ester (Ia~
and 4-(3',5'-dichloropyridyl~2'-oxy)-a-phenox~thioFropionic
acid propargyl eqter (Ib), processes for the production
thereof and the us thereof as selectîve hPrbicides, are
described in European paten~ publica~ion 3114.
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It is known that dicot weeds, and also a number of mono- ~
cots, can o~nbe successfully controlled postemergence in
cereals with 3-(3'-chloro-4'-methylphenyl)~ dimethylurea
(Chlortoluron) of the formula IIa
T~ C-~ ~o-N~I-CO~ ) (IIa)
.~.
Cl
.
or with 3-(3'-chloro-4'-methoxyphenyl)-1,1-dimethylurea
(Metoxuron) of the form~la IIb
3 0 ~ NH-C0-N(C~3)2 (IIb)
Cl
:or with 3-(4'-isopropylphenyl)~ dimethylurea (Isoproturon)
of the formula IIc
._.
7C3~ C0 ~(CS3) 2 (IIc)
., .
or with l-benzothiazol-2-yl-1,3-dimethylurea
(Methabenzthiazuron) of the ormula IId
CEI3
N-C0-NH-Ca3 ( IId)
: .
or with 4~hydroxy-3,5-diiodobenzonitrile (Ioxynil) of the
.~ formula IIe
',, .
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.. .
.. ~
6~8il
-- 3 --
!~ /OH
li i (IIe)
or with 3,5-dibromo-4-hydroxybenzaldehyde-0-(2',4'-
dinitrophenyl)-oxime ~Bromophenoxime) of the formula IIf
Br
E10~ N-O-~ NO2
~: Br ~72
~,
The compounds of the formulae IIa to IIf and their
herbicidal activity are described e g. in the following
publications:
Chlortoluron (compound IIa) in C.~. 5e Conf. Com. franc.:
Mauvaises Herbes (COLUMA), 1969, II3 3493
Metoxuron (compound IIb) in Z. Pflkrankh.,
PflPath., PflSchutz, 1968, 75, 233,
Isoproturon (compound IIc~ in German Offenlegungsschrift 2 107 774,
Methabenzthiazuron (compound IId) in P1Schutz-Nachr. Bayer3
1969, 22, 314,
Ioxynil (compound IIe) in Nature, Lond., 1963, 200, 28~ and
; Bromofenoxime (compound IIf) in Proc, 3rd EWRC Symp.
~- "New Herbicides", Paris, 1968, S. 177.
Surprisingly3 it has now been ound that a
combination o:E both classes of compound X nd II, in a ratio
varing within specific limits, exerts a spe~ific synerglstic
~ action which is able to control the majority of all weeds
;~ ; in cereals without damaging these latter. The principal
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weeds i.n cereals, such as species of the dicot genera Chrysenthemum and Sinapis
as well as certain Avena (wild oat) species, are selec-tively destroyed in the
emergent crops.
Accordingly, the invention provides a synergistic composition for selec-
tively controlling weeds, which composition comprises, on the one hand, a 4-(3',~
5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl ester of the Eormula
~: I
Cl
Cl-- ~ ~0~ O-CH-CO-Z-CH -C-CH (I) ,
o=1~
wherein Z is oxygen or su].fur, and, on the other, in approximately equal ratio to
:~ 10 or in excess of component I, one of 3-(3'-chloro-4'-methylphenyl)-1,1-dimethyl-
urea (IIa), 3-(3'-chloro-4'-methoxyphenyl)-1,1-dimethylurea (IIb), 3-(4'-isopro-
.-. pylphenyl)-l,l-dimethylurea (IIc), l-benzothiazol-2-yl-1,3-dimethylurea (IId),
. 4-hydroxy-3,5-diiodobenzonitrile (IIe) or 3,5-dibromo-4-hydroxybenzaldehyde-0-
(2',4'-dinitrophenyl)-oxime (IIf), together with carriers and/or other adjuvants.
. It is surprising that the combination of a compound of the formula I
with a compound of the formula II not only brings about an expected additive
. . .
r enhancement of the activity spectrum against the customary weeds associated with
cereals and soybeans, but gives rise to a synergistic effect which potentiates
the action of both componen-ts from two points of view.
On the one hand, the rates of application of the single compounds I and
. II are distinctly reduced while the same good action is retained. On the other
;.~ hand, the combination also achieves a high degree of weed control where bo-th sin-
gle compounds have become totally ineffective at too low rates of application.
The consequence is a substantial broadening of the activity spectrum against
~` weeds and an additional increase in the safety margin on application to crops of
cereals and soybeans, as is necessary and desirable in the event of unintentional
- 4 -
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.
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` overapplication.
In addition to beiny used in crops of soybeans and cereals such as bar-
ley, rye and, in particular, whea-t, the composition of -this invention can also be
used for selectively controlling weeds in crops of othe~ monocot plants having
similar sensitivity to herbicides and similar weed infestation, e.g. in mai~e and
rice.
The herbicidal combination emp]oyed in the practice of -this inven-tion
will contain a compound of the formula I and a compound of the Eonnula II in
equal amounts or with an excess of the component II. The preferred ratio o~ com-
ponen-t I to component II is 1:1 to 1:25, with the most preferred ratio being from
1:1 to 1:10.
The herbicidal combina-tion has an excellent action against weeds with-
out having any noticeable effects in crops of cereals when used in the conventio~
nal rates of application of 0.2 to 4 kg/ha, preferably 0.5 to 3 kg/ha.
The following combinations have proved particularly effective synergis-
tic herbicidal mixtures:
a) 4-(3',5'-dichloropyridyl-2'-oxy)--phenoxypropionic acid propargyl
ester (Ia) and 3-(3'-chloro-4'-methylphenyl)-1,1-dimethylurea (IIa),
b) 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxythiopropionic acid propargyl
ester (Ib) and 3-(4'-chloro-4'-methylphenyl)-1,1-dimethylurea (IIa),
` c) 4-(3',5'-dichloropyridyl-2'-oxy)-~-phenoxypropionic acid propargyl
-- ester (Ia) and 3-(4'-isopropylphenyl)-1,1-dime-thylurea (IIc), and
~:i d) 4-(3',5'-dichloropyridyl-2'-oxy)-~phenoxythiopropionic acid propargyl
ester (Ib) and 3-(4'-isopropylphenyl)-1,1-dimethylurea ~IIc).
The present invention also relates to the use of the composition, i.e.
to a method of selectively controlling grasses and weeds postemergence in cereals.
."' ~
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I :~ 6~8/i
In addition to the novel combina-tion of active ingredients, the composi-
tion of this invention also contains suitable carriers and/or other adjuvan-ts.
These can be solid or liquid and correspond to -the substances ~onventionally
employed in the art of formulation, e.y. natural or regenerated mineral substan-
ces, solvents, dispersants,
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-- 6 --
wet~ing agents, ~acki~iers, thickeners, binders or
fertilisers. Suitable formulations are therefore e.g.
emulsifiable concentrates, directly sprayable or dilutable
solutions, dilute emulsions, wettable powders, soluble
powders, dusts, granulates, and also encapsulations in e.g.
polymer substanc~s. The method~ of application, such as
sprayi~g, atomising, dusting, scattering or pouring, are
chosen in accordance with the intended objectives and the
prevailing circumstances, just like the nature of the
co~positions~
The formulations, i.e. the compositions or
preparations containing the herbi.cidal combina~ion
o~ the invention and, where appropriate, a solid or liquid
adjuvant, are prepared ill known manner, e~g. by homogeneously
mixing and/or grinding the active ingredients with
extenders, e.g. solvents, solid carriers and, where
appropriate, surface-ac~ive compounds (surfactants).
Suitable solvents are: aromatic hydrocarbons,
prefexably the fractions cont~ning 8 to 12 carbon
atoms, e.g. xylene mixtures or cubstituted naphthalenes,
phthalate~ ~uch as dibutyl phthalate or dioctyl phthala~e,
alipha~ic hydrocar~ons such as cyclohexane or parains,
alcohols and glycols and their e~hers and esters, such as
ethanol, ethylene glycol, ethylene glycol monomethyl or
monoethyl ether, ketcnes such as cyclohexanone, strongly
polar solvents such as N-methyl~2-pyrrolidone, dimethyl
sulfoxide or dimethyl formamide, as well as epoxidised
vegetable oils such as epoxidised coconu~ oil or soybean
oil; or w ter.
The solid carriers used e.g. for dusts and
dispersible powders are normally natural mineral filler3
such as calcite, talcum, kaolin~ montmorillonite or
attapulgiteO In order to improve the phy~ical properties
it is also possible to add highly dispersed silicic acid
or highly dispersed absorbent polymers. Suitable granula~ed
adsorptive carriers are porous types, for example pumice,
broken brick, sepiolite or bentonite; and suitable
nonsorbent carriers are materials such as calcite or sand.
In addition, a great number of pregranulated materials of
inorganic or organio nature can be used, e.g. especially
dolimite or pulverised plant residues.
Suitable surface-active compounds are
nonionic, cationic and/or anionic surfactants having good
emulsifying, dispersing and wetting properties. The term
"~urfactants" will also be unders~ood as comprising
~urfactant mixtures.
Suitable anionic surfactants can be both water-
soluble soaps and water-soluble 3ynthetic surface-active
compounds .
Suitable soap~ are the alkali metal salts, alkaline
earth metal salts or unsubs~ituted or substituted ammonium
salts of higher fatty acids (C10-C22), e.g~ the sodium or
potas~um salts of oleic or stearic acid, or of natural
fatty a~id mix ures which can be obtained e.g. from coconut
oil or tallow oil. Mention may also be made of fa~ty acid
methyltaurin salts.
More frequently, however, so-called syntheti~
surfactants are used, especially fatty sulfonates, fatty
sulfates, sulfonated benzimida201e derivatives or alkyl-
arylsulfonategJ
q
-- 8 --
The fatty sulfonates or sulfates are usually in the
form o~ alkali metal salts, alkaline earth metal salts or
unsubstituted or substituted ammonium salts and contain a
C8-C22alkyl radical which also includes the alkyl moiety o~
acyl radicals, e.g. the sodium or calcium salt o~ ligno-
sulfonic acid, of dodecylsulfate or of a mixtuxe of fatty
alcohol sulfates obtained from natural ~atty acids. These
compounds also comprise the salts of sulfuric acid esters
and sul~onic acids of adduct~ of fatty alcohols and ethylene
oxide. The ~ulfonated benzimidazole derlvatives preerably
contain 2 sul~onic acid groups and one fatty ac~d radical
containing 8 to 22 carbon atoms. Exampl s o~ alkylarylsulf~
onates are the sodium, calcium or triethanolamine salts o~
docecylbenzenesul~onic acid, dibutylnaphthalenesulfonic acid,
or o~ a naphthalenesulfonic acid/formaldehyde condensatio~
product~ Also suitable are corresponding pho~phates, e.g.
salts of the phosphoric acid ester o an adduct of
p-nonylphenol with 4 to 14 moles of ethylene o~ide.
~ on-ionic surfac~ants are pre~erably polyglycol
ether derivatives o~ aliphatic or cycloaliphatic alcohols,
or sat~rated or unsatura~ed fatty acids and alkylphenols,
~ald derivatives containing 3 to 30 glycol ether groups
and 8 to 20 carbon atoms in ~he (aliphatic) hydrocarbon
moiety and 6 to 18 carbon atoms in the alkyl moiety of the
alkylph nols.
Further ~uitable non-ionic Qurfactants are t~e
water~solu~le adducts of polyethylene oxide with poly-
propyle~e glycol, ethylenediamlnepolypropylene glycol and
alkylpolypropylene glycol containing 1 to 10 carbon atoms
in the aIkyl chain, which adduc s contain 20 to 250 ethylene
glycol ether group and 10 to 100 propylene glycol ether
3 8 ~
g
group3. These compounds usually contain 1 to 5 ethylene
glycol units per propylene glycol unit.
Representative examples o~ nPn-ionic s~rfactants
are nonylphenol-polyethoxyethanols, castor oil polyglycol
ethers, polypropylenelpolyethylene o~ide adducts, tributyl-
phenoxypolyethoxyethanol, polyethylene glycol and octyl-
phenoxypolyethoxyethanol. Fatty acld esters of polyoxy-
ethylene sorbitan and polyoxyethylene sorbitan trioleate
are also suitable non-ionic suractants.
Catio~ic ~ur~actants are preferably ~uaternary
ammonium salts which contain, as N-sub~tituent, at least one
polyglycol ether or C8-C22alkyl radical and, a further
sub~ituents, lower unsubstituted or halogenated alkyl,
benzyl or lower hydroxylalkyl radicals. The
salts are preferably in the ~orm of halide~ methylsulate3
or ethylsul~ates, e.g. stearyltrimethyLammonium chloride
or benzyldi(2-chloroethyl)ethylammonium bromide.
The sur~actants customarily employed in the art
of formulation are described e~g. in th~ following
publications: "McCu~cheo~'~ Detergents aad ~mulsifiers
Annual", MC Publishing Corp., Ringwood, New Jersey, lg79;
Sisaly and Wood, I'Encyclopedia of Surfac~ Active Agents",
Chemical Publishing Co. Inc., ~ew York, 1964.
The concentration of active ingredient in commercial
compssitions is from 0.1 to 95 % by weight, prPferably from
1 to 80 % by weight.
- 10 -
Pre~erred formulations are composed in par~icular
of ~he following constituent~ (/0 ~ perc~n~age by weight):
Solutions
.
active ingredient:5 to 95%, preferably 10 to 80%
solvent:95 to 5%, preferably 90 to 0%
surfactant:1 to 30%, preferably 2 to 20%
active ingredient:10% to 50%, pref~rably 10 to 40%
surfactant:5% to 40%, preferably 10 to 20%
liquid carrier:20% to 95%, preferably 40 ~o 80%
Dust
active ingredient:0.5 to 10%, preferably 2 to 8%
solid carrier:99.S to 90%, preerably 98 o 2%
active ingredient:5 to 75%, preferably 10 to 50/0
wa~er:94 to 25%, pre~erably 90 to 30%
surfactant:1 ~o 40%, preferably 2 to 30%
Wet~ablel~owders
active ingredient:5 to 90%, pre~erably 10 ~o 80% and,
most preferably, 20 to 60~
surfactant:0. 5 to 20%, preferably 1 to 15%
solid carrier:5 to 90%, preferably 30 'co 70%
Granulates
aotive ingredient:0.5 to 30%, preferably 3 to 15%
solid carrier:9905 to 70%, prefer~bly 97 to 85%.
~ ~6~3~38ll
Whereas commercial products will be preferably
formulated as concentrates, the end user will normally
employ dilute formulations. The ~ormulations can be diluted
to a concentration as low as 0.001%.
The compositions of the invention can be mdxed
wlth other biocidal compounds or compositions. Accordingly,
in addition to containing the comlpounds of the general
formula I and ~ormula II~the compositions o~ the invention
can also contain e.g. insecticide,s, fungicides, bactericides,
fungistats~ bacteriostats, or nematocides7 in order to
broaden the activity spectrum.
Herbicides ~lways have a ~ynergistic effect if the
herbicidal action of the c~mbination of I + II is greater
than the sum of the action of the individual active
ingredient~.
The expeeted plant growth E for a give~ combinatio~
of two herbicides can be calculated as follows (cf. COLBY,
S.R., "Calcula~ing ~ynergistic and antagonis~ic respon~es
of herbicide compo~itions'9, Weeds 15, pages 20-22~1967~:
wherein 100
X - the percentage grawth (compared with untreated plants)
after treatment with a herbicide I at a rate of
application of p kg per hectare,
Y ~ the percentage growth after ~reatment with a herbicide
II at a rate of application of q kg per hectare, and
E - the expected percentage growth (compared with the
control pla~ts) after treatment with the herbicidal
mixture of :C ~ II at a rate o application of p ~ q kg
of active ingredient per hectare~
~ ~ 6~3~ li
- 12 -
If the actually observed value is lower than the
expected value E, then thare is s~nergism.
The synergistic effect of the combinations of
compounds I and II is demonstrated in the following
Examples.
.~ 6 ~ 8
~ 13 -
Example 1:
The test plants are sown, in a greenhouse, in plastic
containers fil~ed with 30 litres of sterilised garden soil.
The plants are then sprayed pos~emergence in the 2- to
3-leaf s~age with an aqueous dispersion of the com~ination
of herbicides. The rat~ of application of the di~persion
is 50 ml/m2 . Evaluation is made after 20 days at 18 i-20C
and a relativs humidity of 60-70%" and daily watering of
the containers. The degree of damage to the plants is
assessed linearly in accordance with the following rating:
1 - plants withered
S - medium damage
9 - n~rmal s~ate.
The following results are obtained with different mixture
ratios and total am~unts of active ingredient:
a) Table l:Tolerance and activity o~ 4-(3',5'-dichloro-
pyridyl-2'-oxy)-a-phenoxypropionic acid propargyl ester
(compound Ia) and compounds lIa to IIf, and mixtures
thereof, when applied pos~-em~rgence: ,
__ _~ l _~ _ ~ ~ :`~ . - 14-
C1 . _ ~ __ _ _ _
~ o _, ~ ~ C`~ ~ ,~ _
.u O ~ C~ ~ a~ ~ ~
Q~ -- u~ . _ : ~ __ _ _
3 o . ~ C`J ~ ~:r ~ ~
~ Ul . ~ ~ ~ ~ ~ _-
e o -~~ __ _ _ _
_ _ _o . C~ ~ ~ O Cl ~
~ O`O ~4 ~ G~ ~ ~
~ o o . _ _ _
__ _ U~, . _ _ _ _ C~l
U~ o . _ _ _ _ _ _
o . ~ _, ~I _, _ _,
O a~ cr o~ ~ ~ cr
W _ U~ l __ .,. ' .; _ _
'w . ~ ~ _, C~ ~ ~
~ U~ o ' . _ _ _ _ _
~ . . C~ ~ _l _, ~ ~,
~ o _, . _ _ ~ _ _
W _ ~ . C~ Cr~ CJ _ ~ 01
~ o o . ~ ;.. _, ~ ~ ~
U~ ~ ~ ~ _. C~l _ ~
__ ~ . _ _ _ _ _ _ .
. . o, . ~ ~. ~ ~ ~
~ o C`~ ~I C`~ ~'I ~ ~`I
O O . __ _ _ _ ~`I
l _ Ul. ~ _ _ _ _ ; C`~
:1 U~ O . _ . ; _ _ ~`I
_~ ~ . _ . _ _ .
_ .... .. . C~ C`l C~ ~.. C~l _Y
u~ ¢~ ~ a~ o~ a~ s~
O O . .,.. , ~.~ ~- _ _
. O cr ~ ~ 5~ c~ ol
_ ___ . _ .. .~ _ _ _
c~ ~ o~ cl~ o~ ~ a~
U7 --O' . _ _ _ ..
_ O O . ~ a~ ~ e~ ,~ ~
~ -- U~ . ~ . _ .. . _
c~ O O . ~o ~o ~ r~ D ~
O__ C~ I;~ ~ ~ ~ ~
O --O- _ _ __ ~ C~ 3
~, ~ æ~ w ., _
: .
.
~6~ 3
- 15 ~
If the valuesrelating to the additi~e action
calculated by the method of Colby are compared with the
results reported in Table 1, then it is evident that the
observed growth figures given for Sinapis arvensis and
Chrysanthemum are lower than those calculated. The
synergistic effect of the combination of 4-(3',5'-dichloro-
pyridyl-2'-oxy)--phenoxypropionic acid propargyl
ester and compounds IIa to IIf is thus demonstrated
(cf. Table 2).
Table 2: Values calculated by the method of Colby for
demonstrating the synergism of 4--(3',5'-dichlo~opyridyl-
2'-oxy)--phenoxypropionic. acid propargyl ester
(com~ound I~) and compounds IIa to IIf.
3 ~ li
- 16 -
. _ ul arr~A pa~ ~a dxa ~ ~ o o ~ ~'_
u~ O a~A pa~a~ap ~ ~ u~ ,~ u~ ~
a~ ~ . - _ _ _ . _
~ o o an[~A pa~a dxa ~_ ~ ~ ~ ~ _,
e ,, ~rrre~ par~la ~3p ~ ~ ~ ~ ,,
___ ~ __ _ _ _ _ _
~e u~ ~rr@~, a dxa ~o_ ~ o ~ ~
o ~n~ p3u~ a~ap ,~ ~ ~ ~ ~ ul
~ u~ _ ............ . __ _ . c _ _
:~ O O rl[BI~ p~ d~ l ~ ~ o ~ ,.
. ____ __ _ _ _
_ __ar~eA p~ 3~aF . _ ~ ~ r~ c~l _
arr[~A pal ~adxa ~o_ ~ _, u~
o 3~ pau~la~ap ~ ~ _,
. __ __ __ _ _ _ _
o o an~ pa~aaxa u~ ~ ~ c~ _,
_, ar~ ~u~ a~aF __ _ _ _ _ _
_ __ ~__ _ _ _ _
anl~A pa~,oa~xa ~o ~ _,
o r~ ap ~ u~ ~ ~ -
~
~u~ ~ _ _ _ _
~ O O 3~ p~ dx~ ~ ~ ,, ~ _, ~
c~ r~~ a~ BA pall~ ~ ~`1 _ _ _ _
__ ~_ __ _ _ __ _ _
u~ all~2A pa~:~adx- ~ ~ ~ ~ ~ ~
O ~A p3tT~mla:lap ~ C~l ~1 C~l c~ ~1
. . . , _ . _ _ ~ _ _
O O II~A pa~,~adxa ~ ~ ~ ~ ~ ~
,~ ~_ _ _ _ _
all~ p~la3,ap ~ ~ ~ ~ ~ _,
.- _ __ ~ _
ta u~ al~A pa~axa
w o ~ _, _, ~_, _, ........... -~
C 3tll~?A ~ p~wla~ap ~ ~ c~l ~ ~ _~
c, u~ __ ~_ _ _ _ _ _
.3 O O arrreA pa~adxa ~ ~ ~ C~l ~
_, a~ A pa~,m~ 3p c~ ~ ~ ~ ~
_ _ __ __ _ _ _ _ _ _
u~ 3n~ pa~adxa u~ u~ ~ u~ ~ u~
. __ _ __ . . . . _
u~ O ~eA p~mla~a ~ 8 o o o o
.
O O ~nlBA pa1 ~dx. ,~ ,~ ,~ u~ u~ r~
3 . _~ an~eA p3~WIa~aF ~` ~ ~ ~ ~
~nleA pa~,~a x._ ~ ~ ~ ~ ~.
o an~A pa~a~ap u~ ~ ~ ~ co ~
r~~ .~ _ _ _ _ _ . I
O O tl~BA pa ~ ~a dx~ ~ ~ ~ ~ ~o
c~ oa~rrLeA paul,n:Ia~aF u~ ~ ~0 u~ ,~ ~3
_ ~ E~__ ~ ~ H ~_1 H u~
L~ a ~ 9 o ~ __ a~ a a~ a~ ~a~ ~
~ 8~/A
- 17 -
b) TabLe 3:Tolerance and activity of 4~(3',5'-dichloro-
pyridyl-2'-axy)-~-pheno~thiopropionic acid propargyl ester
(compound Ih) and compounds IIa to IIf, and mdx~ure~
thereaf, when applied post-emergence:
3 8 ~
_ _ ~ _ _ __ _ - 18 -
~ ~ ~ I ~ ~ ~
U~ . . . _ _ _ . _ _
~ . ~r ,~ ~ ~o c~l _~
6 O _. . _ _ _ _ _
c~ a~ cl ~ ~ ~1 o~
~ _ U~ . __ _ _ _ _
o . ~ ~ I C~l `O c~ ~'1
U=~ _. _ j. . _ __
~ U~. C`~ ~ C~l ~o ~ _~
O _~ . __ __ _-.
.~ C~ :J~ C~ ~ 5~ ~ Cl~
C _ ~ l _ _ _ _. __
~ . ~.:3 ~ V~ ~ ~r ~
~C:l , _ _ _ _, . _
I~ O ~
. ~ ~ ~ `t O~ ~
_-- u~ : __ _ _. _ _
O ~ ~ _~ ~ _~ ~
Ul ,. , __ _ _. . .
e~ . C~l ~ _l _l _l
O _~ , . _ _ _ _~ .. . _
O c~ ci~ a~ cr~ a~ ~
o~ -- U~ l _ _ _ _. _ _
._~ . ~ ~'7 _ ~ ~ ~1
C U~ ~ . _ , _. _
~ .. C~l ~ ~ _~ _I ~
~ O ,_1 . _ _ . __ ~
o~ ~ a~ ~ 5~ o~
__ __ l _ _ _ _ _ _
.~ Ul ~o ~ ,-1 ~ C~l
,C O' ~. __ _ . _
V~ . ~ C`~ ~ ~ _~ ~
__ ~1 , _ __ ,,._. _ _
. c`J ~ ~ ~ ~ c`l
u~ o ~ - - - :- -- -
~ . c`l c`l ~ ~ ~ ~
~~ ~------ ----
o c`~
- ~ l - - - - - -
. c`l ~ ~ c'~ ~ ~
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~ . . ~ ~ ~ c`l ~ ~
'3 o -~ l - - - - - -
o ~ c`
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cC~ u~ a~ ~ cn O~ :n
~ o o l------------
o c~ ~ l~ ~ ~ o~
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a~ ~ ~ co
u~ o l - ~- - - -
. . ~ ~ ~ c~ cr~ o~
o -l ~ - - -
~ ~ ~ r~ r~ ,~ r~ ~
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a~ . ,~ cr. a~ ~ ~ 5~
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- o -~ ~ ~ x ~ ~ cr~
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S~ O r. I~ r~ r~ r~ I~
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o a~ a~
c~ o - - - - - - - -
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~ su - s~ ~ ~ u ~ c) u~
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~l ~1 O hn O O hD O O O O O O
; ~ ~_ c~5~ c~ '~ ~ ~ ~ c~ Q~
1 3 B~3~3li
- 19 -
If the values relating to the additive action
calculated by the method of Colby are compared with the
results reported in Table 3, then it is evident that the
observed growth figures given for Sinapis arvensis and
Chrysanthmum segetum are lower than those calculated. The
synergistic effect o~ the combination of 4-(3',5'-dichloro-
pyridyl-2'-oxy)-~-phenoxythiopropionic acid ester
(compound Ib) and compounds IIa to IIf is thus demonstrated
(cf. Table 4).
Table 4: Values calculated by the method of Colby for
demonstrating the synergism o~ 4-(3',51-dichloropyridyl-2'-
oxy)-~-phenoxypropionic acid propargyl ester (compound Ia)
and compounds IIa to IIf.
- ~ 3 ~3~/i
- 20 ~
_~ _ __ ~ _ ~ _ _
u~ ~ p~adx~ ~ ~ ~ ~ ,~ u~
~ o ~P _ _ _ o ' _ _
U U~ . ~ _ ~ ~ ~ ~ .~ C`J
~,o ~ an~l~ p~aaxa ~ ~ r- ~3 ~
o o__ ~O_ _, ~ . _, _,
~ _ _1~ P~ P ~ _ ~ ~o ~ _,-
an~ pa~ aa dxa ~ ~ o ~1 ~ ~
~ u~ ~ ~L ~o u~ . ~ .. ~_
u O i~lleA ~3~11;~;3p . u~ ~1 ~ e~l ~`1
~ U~ __. __ __ __ _
8 O O ~ A pe~ dx~ ~_ ~ ~ 8
- - ~ ~ ~ ~ ~ ~
o an~eA_p~ dx~
~T~?A Feu~;E:ap ~ ~ _,
. __ _ _ _ . _
v. o o 3rr[~A pa~oadxa ~ ~ _. ~ _ ,
e anleA pa~m3la~al ~ ~7 _, _~ _, ~ .
an~pA pa~oa a ~ u~ ~ u~ ~ u
O aT~A E~:l~;~
o~~ - - ~ - - ~ - - -
e o o an eA pa~oadxa ~ ~ _, ~ _, _-
u~ _~ ar~ peul~a~p ~ . ~ _~ _, _. ~
_ _ __ __ _ _ _ _ _ _
~ arrreA pa~ dxa c~l ~ ~ ~L
Ul --ar[ eA pau~3~ap c~ ~ _~ _; ~
O O 7rl~A pa~,~adxa ~ ~ ~ ~ ~ ~
. ~ _____
~ _, a~A p~a:~3p ~ ~ ~ ~ ~ e~l
3 _ . _. ~_ _ _ ___
n~ p~adx~ ~ ~ ~ ~ ~ ~
0 o ar~BA P~F _ _ _ ~ _ _
C It7 _~ ,___~_ d _ _ _'1 d _I
:~ . arE~A pa~aaxa C~l ~ ~ . c~
<d O O ~ _~ _l c~ ~ _~ _l
__ _ an~A paUI~ =;aF ~ ~ _, ~ ~ _.
U~ a~A pa:~adx~ U~ U~ ~ ~ u~
U ~ O ~n~BA E~3Ullll:l~p oo O o ~ O 8
~d o o ~ 7~ U~ _;~ o U~
_- ~r{ eA E~ a~ap o _~ o r~ _~ 8
_ __ __ _ _ _ . _ _ _
_ u~ ~nlsA p~aax~ u~ ~ u~ u~ u~ u~
P u~ o a~[eA pa~m~a~ r~ ~ ,~ _~
o o all~A pa~dx
F ~1_ ~ ~i oo ~ ~ 5
~ ~ ~ ~, ~ ~ ~ ~ ~
~ ~ ~ ~ e ~ ~ ~ ~ ~
E~ ~ 0 00 O 0 ~0 O O O O O O
:; _ ~ ~ __ ~ C~ C~ ~ ~ ~
~6
- 21 -
Example 2: Field tests in wheat ~ields yielded the following
results. The growth figures are reported as percentages
compared with the untreated control field.
a) Field test in Cisse/France.
Applica~ion on March 18, 1980.
Evaluation 85 days after application (June 10, 1980).
Compound ~wth of AVENA FATU~ Growth of
rate of appl~- ~bserved expected accord- WHEAT
cation in g/ha _ ing to COLBY __
Ia: 150 50 _ 100
Ib: 200 55 ~ 100
IIa:2000 60 _ 100
IIc:1250 90 _ 100
Ia +}Ia: (150 + 2000) 12 30 100
Ia +IIc: (150 ~ 1250) 6 45 100
Ib +IIa: (200 + 2000) 12 33 100
Ib ~IIc: t200 ~ 12S0) S 50 _ ___
b) Field test in Pouant/France.
Application on ~arch 19, 1980.
Evaluation 84 days after application (June 10, 1980~.
. _ . . . ~ ~
Gompound Growth of AVENA FATU~ ~rowth of
rate of appli~ observed expected accord- WHEAT
- _ in~to COLBY ____________
Ia: 150 15 _ 100
Ib: 200 20 _ 100
IIa: 2000 80 _ 100
IIc: 1250 70 _ 100
Ia + lIa:(150 + 2000) 2 12 100
la + IIc: (150 t- 1250) O 10.5 100
Ib I IIa: (200 + 2000) 3 16 100
Ib + IIc: (200 + 1250) 2 12 100
. .. _ .. ,, __. . ...
3 8
- 22
Formulation Examples
Exampl _
Forcu~l~ [l~ c6~ for syner~istic mixtures
of the ~ormulae I and II (throughout1 percentages are by
weight)
a) Wettable powders a) b) c) d)
compound Ia or Ib 10 % 20 % 5 % 30 %
one of compounds IIa to IIf 10 % 40 % 15 % 30 %
sodium lignosulfonate S % 5 % S % 5 %
sodium laurylsulfate 3 ~/0 - 3 %
sodium diisobutylnaphthalene-
sulfonate - 6 % - 6 %
octylphenol polyethylene
glycol ether (7-8 moles o
ethylene oxide) - 2 % - 2 %
highly dispersed silicic acid 5 % 27 % 5 % 27 %
kaolin 67 % - 67 %
The active ingredient mixture is t ~ oughly mixed with the
adjuvants and the mixture ~ ~roughly ground in a suitable
mill~ affording wettable powders which can be diluted with
water to give suspensions of the desired concentration.
b) Emulsifiable concentrates a) b) c)
compound Ia or Ib 5 % 5 % 12 %
one of compounds IIa to IIf 5 % 20 % 13 %
octylphenol polyethylene glycol ether
(4-5 moles of ethylene oxide) 3 % 3 % 3 %
calcium dodecylbenzenesulfonate3 % 3 % 3 %
castor oil polyglycol ether
(36 moles o~ ethylene oxide) 4 % 4 % 4 %
cyclohexanone 30 % 30 % 30 ~/0
xylene mixture 50 % 35 % 35 %
Emulsions of any required concentration can be obtained from
these concentrates by dilution with water.
I~ --
- 23 -
~) Dusts a) b) c~ d)
compound Ia or Ib 2 % 4 % 2 % 4 %
one of compounds IIa to IIf 3 % 4 % 4 ~/0 8 %
talcum 95 % - 94 %
kaolin - 92 % - 88 %
Dusts which are ready for use are obtained by mixing the
active ingredient mixture with the carriers~ and grînding
the mixture in a suitable mill.
d) Extruder ~ranulates a) b) c)
compound Ia or Ib 5 % 3 % 5 %
one of compounds IIa to IIf 5 % 7 % 15 % .
sodium lignosulfonate 2 % 2 % 2 %
carboxymethylcellulose 1 % 1 % 1 %
kaolin 87 % 87 % 77 %
The active ingredient mixture is mixed and ground with the
adjuvants, and the mixture is subsequently moistened with
water. The mixture is extruded and then dried in a stream
of air.
e) Coated granulates a) b)
compound Ia or Ib 1.5 % 3 %
one of compounds IIa to II 1.5 % S %
polyethylene gly~ol 200 3.0 % 3 %
kaolin 94.0 % 89 %
The finely ground active ingredient mixture is uniformly
applied, in a mixer, to the kaoLin moistened with poly-
ethylene glycol. Non-dusty coated granulates are obtained
in this manner.
..
.
I ~
`` I 3 ~ 8 '~
- 24 -
f) ~ es a) b)
compound Ia or Ib 20 % 20 %
one of compounds IIa to IIf 20 % 40 %
ethylene glycol . 10 % 10 %
nonylphenol polyethylene glycol ether
(15 moles of ethylene oxide) 6 % 6 %
sodium lignosulfonate 10 % 10.0 %
carboxymethylcellulose 1 % 1.0 %
37 % aqueous formaldehyde solut:ion 0.2 % 0.2 %
silicone oil in the form of a 75 %
aqueous emulsion 0.8 % 0.8 %
water 32.0 % 12.0 %
The finely ground active ingredient mixture is intimately
mixed with the adjuvants, giving a suspension concentrate
from which suspensions o any desired concentration can be
obtained by dilution with water.
,.
