Note: Descriptions are shown in the official language in which they were submitted.
1 3 ~3~9
~ he invention relates to new herbicidal synergistic combinations which
consist of a certain triazinedione and of certain cereal herbicides.
It has already been disclosed that l-amino-3-(2,2-dimethylpropyl)-6-
ethylthio-1,3,5-triazine-2,4-(lH,3H)-dione can be used as a herbicide (see, for
example, Danish Patent Specification 136,067).
It is also knc~n tha-t the active compounds mentioned belcw can be used
as cereal herbicides (see, for example Chemie der Pflanzenschutz- und Schadlings-
bekampfungsmittel (Chemistry of Plant Protection Agents and Agents for Combating
Pests), volume 5 "Herbizide" ("Herbicides"), Springer-~erlag (1977): certain
ureas (such as chlorotoluron, isoproturon, linuron, methabenzthiazuron and
metoxuron), certain thiolcarbama-tes (such as dialla-te and triallate), certain
carboxylic acid esters (such as benzoylprop-ethyl, chlorfenprop-me-thyl, diclofop-
methyl, flamprop-methyl and flamprop-isopropyl), certain benzoic acids (such as
dicamba), certain benzonitriles (such as bronoxynil and ioxynil), certain phenol
derivatives (such as DNOC, dinoterb and dinoseb acetate), oe rtain dinitroanilines
(such as pendimethalin and trifluralin), certain diphenyl ethers (such as
nitrofen), certain phenoxyalkanecarboxylic acids (such as 2,4-D, 2,4-DP, MCPA and
MCPP), certain s-triazines (such as cyanazine, simazine and terbutryn), certain
as-triazin-5-ones ~such as isomethiozin and metribuzin) and oe rtain other hetero-
cyclic active compounds, in particular bentazon and difenzoguat.e abovementioned active compounds (which are called by their common
names) indeed exhibit a good tolerance in cereal crops, for example in wheat and
barley, but they display certain weaknesses when used against important weeds and
grasses.
According to the present invention there is now provided a new
herbicidal composition containing as active ingredients
(I) l-amino-3-(2,2-dimethylpropyl)-6-ethylthio-1,3,5-triazine-2,4(1H,3~)-
dione of the formula
-- 1 --
~,
:
~3:LOg
(CH3)3C-CH2-N N N 2 (I)
o N SC2H5
and (II) one of the active oompounds mentioned kelcw from the cereal herbicide
; group, that is to sa~ either
(1) one of the follcwing ureas: (a) N'-(3-chloro-4-methylphenyl)-N,N-dimethyl-
~ urea (chlorotoluron) ("la"), (b) N'-(4-isopropylphenyl)-N,N-dimethylurea (iso-
: proturon) ("lb"), (c) N'-~3,4-dichlorophenyl)-N-methoxy-N-methylurea (linuron)
("lc"), (d) N-benzothiazol-2-yl-N-methyl-N'-methylurea (methabenzthiazuron)
("ld") or (e) N'-(3-chloro-4-methoxyphenyl)-N,N-dimethylurea (metoxuron1 ("le")
or
(2) one of the follcwing thiolcarbamates: (a) S-2,3-dichloroallyl diisopropyl-
thiolcarbamate (diallate) ("2a") or (b) S-2,3,3-trichloroallyl diisopropylthiol-
carbamate (triallate) ("2b"); or
(3) one of the following carboxylic acid esters: (a) ethyl N-benzoyl-N-(3,4-di-
:chlorophenyl)-2-aminopropionate (benzoylprop-ethyl) ("3a"), (b) methyl 2-chloro-
: 3-(4-chlcrophenyl) propionate (chlorfenprop-methyl) ("3b"~, (c) 2-[4-(2,4-
dichlorcphenoxy)-phenoxy~-propionic acid methyl ester (diclofop-methyl) ("3c"),
(d) methyl N-benzoyl-N-(3-chloro-4-fluorophenyl)-2-aminopropionate (flamprop-
~: methyl) ("3d") or (e) isopropyl N-benzoyl-N-(3-chloro-4 fluoro-phenyl)-2-amino-
propionate (flamprcp-isopropyl) ("3e"); or
(4) the follcwing benzoic acid derivative: (a) 2-methoxy-3,6-dichloro-benzoic
acid (dica~ba) ("4a"); or
(5) one of the following benzonitriles: (a) 3,5-diiodo-4-hydrnxy-benzonitrile
~: (ioxynil) ("Sa") or (b) 3,5-dibromo-4-hydroxy-benzonitrile (bromoxynil) ("5b");
or
- 2 -
~,...
`~-lt
~ .
,
: :
I 1 63 lOg
(6) one of the follcwing phenol deriv~tives: (a) 2-methyl-4,6-dinitrophenol
(DNOC) ("6a"), (b) 2,4-dinitro-6-tert.-butylphenol (dinoterb) ("6b") or (c)
2-sec.-butyl-4,6-dinitrophenyl aoe tate (dinoseb acetate) ("6c"); or
(7) one of the following dinitroanilines: (a) N-(l-ethylpropyl)-3,4-dim~thyl-
2,6-dinitroaniline (pendimethalin) ("7a") or (b) N,N-di-(n-propyl)-2,6-dinitro-4-
trifluoramethyl-aniline (trifluralin) ("7b"); or
(8) the following diphenyl ether: (a) 2,4-dichlorophenyl 4-nitrophenyl ether
(nitrofen) ("8a"); or
(9) one of the fol~owing phenoxyaIkanecarbaxylic acids: ~a) 2,4-dichloropheno~y-
acetic acid (2,4-D) ("9a"), (b) 2,4-dichlorophenox~propionic acid (2,4-DP~ ("9b"),
(c) 4-chloro-2-methylphenoxyaoetic acid (~CPA) ("9c") or (d) 2-(2-methyl-4-chloro-
phenoxy)-propionic ad d (MCPP, mecoprop) ("9d"); or
(10) one of the following s-triazines; (a) 2-chloro-4-ethylamino-6-(1-me-thyl-1-
cyanoethylamino)-s-triazine (cyanazine) ("lOa"), (b) 2-chloro-4,6-bi~-(ethylamino)-
s-triazine (simazine) ("lOb") or (c) 2-ethylamino-4-methyl-thio-6-tert.-butylamino-
s-triazine (terbutryn) ("lOc"); or
(11) ane of the following as-triazin-5-anes: (a) 4-N,N-isobutylimino-6-tert.-
butyl-3-(methylthio)-as-triazin-5(4H)-one (isomethiozin) ("lla") or (b) 4-amino-
6-tert.-butyl-3-(methylthio)-as-triazin-5(4H)-one (me-tribuzin) ("llb"); or
(12) one of the following heterocyclic active campounds: (a) 3-isopropyl-2,1,3-
benzothiadiazin-4-one 2,2-dioxide (bentazon) ("12a") or (b) 1,2-dimethyl-3,5-
diphenyl-pyrazolium methyl-sulphate (difenzoquat) ("12b"), in admixture with a
solid diluent or carrier or in admixture with a liquid diluent or carrier cantain-
ing a surface active agent.
The new active compound comhinations of the present invention have a
particularly broad herbicidal activity in various crops, in particular in cereal
crops.
-- 3 --
~"
~3~3:10~
Surprisingly, the activity of the active compcund combinations accord-
ing to the invention is considerably more powerful than the sum of the actions of
the individua] active compounds. A true synergistic effect which could not be
predicted is present, and not only a supplementary action~ The new active com-
p~und combinations thus represent a valuable enrichment of selective herbicides,
in particular of cereal herbicides.
Examples which may be mentioned of weeds which in general occur as a
contaminant in cereal crops and which can reliably be co~bated by the acti~e com~
pound combinations according to the in~ention are:
dicotyledon weeds of the genera Sinapis, Lepidium, Galium, Stellaria,
Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus,
Portulaca, Xanthium, Convolvulus, Ip2moea, Polygonum, Sesbania, Ambrosia, Cirsium,
Carduus, Sonchus, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex,
Datura, Viola, Galeopsis, Papaver, Centaurea and Solanum; and
monocotyledon weeds of the genera Echinochloa, Setaria, Panicum, Digitaria,
Phleum, Poa, Festuca, Eleusine, Brachi æ ia, Lolium, Bromus, Avena, Cyperus,
Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis,
Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, AloFecurus
and Apera.
EIowever, the use of the active compound combinations according to the
invention is in no way restricted to these genera, but also extends in the same
~anner to other plants.
The new active cc~pound combinations are particularly suitable for cGm~
bating weeds in the wheat and barley varieties of cereal.
The synergistic effect of the active compound combinations according to
the invention is particularly highly pronounced at oe rtain concentration ratios.
~Iowever, the weight ratios of the active compounds in the active compound combina-
- 4 -
`3 1 ~ 0 ~
tions can be varied within relatively wide limits. In general, 0.5 to 10 parts
by weight, preferably 0.5 to 5 parts by weight, of active co~pound from the
active compound group (II) are present per part by weight of active co~pound of
the formula (I).
rrhe active compound ccmbinations accord mg to the invention can be con-
verted to the customary formulations, such as solutions, emulsions, -~ettable
powders, sus~ensions, powders, dusting agents, pastes, soluble powders, granules,
suspension-emulsion concentrates, natural and synthetic materials impregnated
with active compound, and very fine capsules in polymeric substances.
These formulations may be produced in known manner, for example by mix-
ing the active cQmpounds with extenders, that is to say liquid or solid diluents
or carriers, optionally with the use of surfaoe -active agents, that is to say
emulsifying agents and/or dispersing agents and/or foam-forming agents. In the
case of the use of water as rm extender, organic solvents can, for example, also
be used as auxiliary solvents.
As liquid diluents or carriers, especially sol~ents, there are suitable
in the main, aromatic hydrocæbons, such as xylene, toluene or alkyl naphthalenes,
chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chloro-
benzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydro-
carbons, such as cyclohexane or p æ æ fins, for exa~ple mineral oil fractions,alcohols, such as butanol or glycol as well as their ethers and esters, ketones,
such as aoetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or
strongly polæ solvents, such as dime-thylformamide and dimethylsulphoxide, as
well as water.
As solid carriers there may be used ground natural minerals, such as
kaolins, clays, talc, chalk, quartæ, attapulgite, montmorillonite or diatomaceous
earth, and ground synthetic ninerals, such as highly-dispersed silicic acid,
-- 5 --
: ~3~3~09
.
alumina and silicates. As solid carriers for granules there may be used crushed
and fractionated natural rocks such as calcite, marble, pu~ice, sepiolite and
dolomite, as well as synthetic granules of inorganic and organic meals, and
granules of organic material such as sawdust, COCQnUt shells, maize cobs and
tobacco stalks.
As enmlsifying and/or foam~forming agents there may be used non i onic
and anionic emulsifiers, such as polyoxyethylene~fatty acid esters, polyoxy-
ethylene-fatty aloohol ethers, for example alkyla~yl polyglycol ethers, alkyl
sulphonates, alkyl sulphates, aryl sul~honates as well as albumin hydrolysis pro-
ducts. Dispersing agents include, for example, lignin sulphite waste liquors andmethylcellulose.
Adhesives such as carboxymethyl oe llulose and natural and synthetic
polymers in the form of pcwders, granules or lati oe s, such as gum æ abic, poly-
vinyl alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to u æ colorants such as inorganic pigments, for example
iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as
alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and tra oe
nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum
and zinc.
m e for~ulations in general contain from 0.1 to 95 per cent by weight
of total active compounds, preferably from 0.5 to 90 per cent by weight.
e active ccmpound ccmbinations according to the invention are in
general used in the form of finished formLlations. However, it is also possible
for the active cc~lpounds contained in the active compound ccmbinations to be
mixed as m dividual form~lations when used, that is to say to be used in the form
d tank mixtures.
The new active compound ccmbinations, as such or in their foxmulations,
- 6 -
.
1 1 B3109
ean also be used as mixtures with other knawn cereal herbieides, finished formula-
tions or tank mixtures again being possible. Mixtures with other knawn active
eompounds, such as fungieides, insectieides, acarieides, nemati d des, bird repel-
lants, growth faetorsr plant nutrients and agents whieh improve soil strueture,
are also possible.
m e ne~ active compound combinations ean be used as sueh, in the form
of their formulations or in the use forms prepared therefram by further dilutian,
sueh as ready-to-use solutions, suspensions, em~lsions, powders, pastes and
granules. They are used in the eustomary m~nner, for example by watering, spray-
ing, atamising, dusting or seattering.
The amounts of aetive eompound eambination aeeording to the inventianapplied ean be varied within a oe rtain range; they depend, inter alia, on the
weather and on soil faetors. In general, the amounts applied are between 0.2 and
8 kg of aetive eompound eambination per ha, preferably between 0.5 and 5 kg/ha.
m e aetive eompound eambinations aeeording to the invention ean be
applied either before or after emergen oe of the plants. m ey can also be ineor-
porated into the soil before sawing.
The present invention also provides herbieidal eamposition cantaining
as active ingredient an active ingredient ccmbinatian of the present invention in
admixture with a solid diluent or earrier or in admixture with a liquid diluant
or earriar containing a surfaae-activa agent.
The present invention also provides a method of combating weed which
camprises applying to the waeds, or to a habitat thereof, a aetive compound camr
bination of tha present invention alone or in tha form of a camposition cantain-
ing as active ingredient an active compound combination of the present invention
in admixture with a diluent or carrier.
The present invantion further provides crops, espaeially cereal crop,
- 7 -
1 1 63 1 09
protected from damage by weeds by being grown in areas in which immediately prior
to and/or during the time of the growing an active compound combination of the
present invention was applied alone or in adm~xture with a diluent or carrier.
It will be seen that the usual methods of provid~ng a harvested crop
may be improved by the present invention.
The good herbicidal action of the novel active compcund co~binatio~s
can be seen from the Examples which follow. Whilst the individual active com-
pounds have weaknesses in herbicidal action, the combinations show a very broad
action against weeds which goes beyond a simple additive action.
A synergistic effect exists with herbicides whenever the herbicidal
action of the active compound combination is greater than that of the individu-
ally applied active compounds.
m e action to ke expected for a given combination of two herbicides
can be calculated as follows (see OOLBY, S.R., "Calculating synergistic and
antagonistic responses of herbicide combinations", Weeds 15, pages 20 - 22, 1967):
If X = ~ damage by herbicide A used in an amount of p kg/ha
and Y = ~ damage by herbicide B used in an amount of q kg/ha
and E = the expected damage by herbicides A and B used in amounts of p
; and q kg/ha
then E = X ~ Y - X . Y.
' ~ 100
If the actual damage is greater than calculated~ the action of the CO~r
bination is superadditive, that is to say it exhibits a synergistic effect.
he examples which ~ollow show that the found herbicidal action of the
active compound oombinations according to the invention on weeds is greater than
~ the caIculated action, that is to say a genuine synergistic effect exists.
:
~ - 8 -
3 :1 ~ 9
Example A
Pre-emergence test
Solvent: 5 parts by ~eight of acetone
Emulsifier: 1 part by weight of aIkylaryl polyglycol ether
To produce a suitable preparation of active compounds, 1 part by weight
of the active ccmpound combination was mixed with the stated amount of solvent,
the stated D unt of emulsifier was added and the concentrate was diluted with
water to the desired concentration.
Seeds of the test plants were sown in normal soil and, after 24 hours,
watered with the preparation of the active compounds. It was expedient to keep
constant the am~unt of water per unit area. m e total concentration of the
active compounds in the preparation was of no importance, only the amount of
active compounds applied per unit area being decisive. After three weeks, the
degree of damage to the plants was rated in % damage in comparison to the develop-
ment of the untreated control. The figures denoted:
0% = no action (like untreated control)
100~ = total destruction
The active co~lpounds, amounts applied and results can be seen from the
table which follows:
:
_ g _
: .
1~3~
o o o o o o o $
o~ln
'no~l O
.~ ~
~, ~ ,
11 ,,
~ ¦ ;~ I . 1 N _~ N ~ ;j N O
: a : ~ - N
b
~ ~ ''
~ H ,~ ~ ~ _ r~
:
10 -
~; ';
- '' ' , '
..
~ ~63109
.Example B
-
Post-emergence test
Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight
of the active compound ccmbinatio~ was mixed with the stated amount of solvent,
the stated amount of emulsifier was added and the concentrate was diluted with
water to the desired concentration.
Test plants which had a heig~lt of 5 to 15 cm were sprayed with the pre-
p æ ation of the active co~,pounds in such a way as to apply the amounts of active
compounds per unit area which were indicated in the table.
m e amount of water applied was 2,000 l/ha. After 3 weeks, the degree
of damage to the plants was rated in ~ damage in comp æison to the develcpm~nt of
the untreated control.
m e figures denoted:
0% = no action (like untreated control)
100~ = total destruction
The acti.ve ccmpcunds, amounts applied and results can be seen from the
: table which follows:
-- 11 --
l~u
I h ~ o u) o
o\o ~ h o o o LO o o o
!~i ~ o LO o ~ ~ '
¦ O ~ ~ ¦ o o 4~ o o ~ ~ ~
~ *. ~ ~
~ ~ Lr~ In ~ ~
~ ~ co ~ ~ ~ ~
~¦ --~ ~ '' ~ ^ ' 9 9 ~ u
~ 1~ I
;~ ~ ~ I ~I N
:: _
~ ~ ~ ~ Z
~ O ~ H ~
-- 12 --
.
'
