Note: Descriptions are shown in the official language in which they were submitted.
O.Z~ 0050/032590
1,3-BIS-(TRIHALO~ETHYLSULFENYL)~IMIDAZOLINE-2,4~DIONES
The present invention relates to new and valuable 1,~-bis-
-(trihalomethylsulfenyl)~imidazoline-2,4-diones and their use
as fungicides.
It is known (E.J. Lien and co-workers, Pestic. Biochem.
and Physiol.g 4~ 289, 1974) that bis S-CC13 derivatives o~
5,5-diphenyl- and 5-ethyl-5-phenylimidazoline-294-dione have
fungicidal properties.
We have now found that new imidazoline-2,4-dione derivatives
of the formula
O R
r~
XCC12-S-N~,,N-S CC12Y
where X and Y are idential or different and each denotes chlorine
or ~luorine, and R1 and R2 are identical or different and each
denotes hydrogen or lower alkyl (C1-C4), or R1 and R2 are directly
linked with each other, or together denote the radical -(CH2)n-,
n denoting one o~ the integers 1, 2, 3, 4, 5 and 6, have a strong
~ungicidal action. I~e new co~pounds have a broad spectrum of
act;on and may be used especially on Phycomycetes and Fungi
imperfecti, but also on Ascomycetes and Basidiomycetes. The
new compounds are for example particularly suitable for protecting
plants against phytopathogenic fungi, e.g., Plasmopara viticola
in grapes, Pseudoperonospora humuli in hops, Phytophthora in-
festans in potatoes and tomatoes, Pythium ultimum in pea seedlingsS
Botrytis cinerea in grapes, strawberries~and pimientos, Septoria
nodorum in cereals, and Venturia inaequalis (scab) in apple ~rees.
-- 1 -- .
.~ ~ .
os
O.Z. 0050/032590
In the concentrations necessary ~or combating fungi, the com-
pounds cause no damage to crop plants.
We have further found that compounds of the ~ormula I are
obtained by reacting an imidazoline-2,4-dione of the formula
O Rl
\~ R2
~N y NH II
- O
with a sulfenyl chloride of the formula XCC12-S-Gl (IIIa) or
YCC12-S-Cl tIIIb), R1, R2, X and Y having the above meanings,
if desired in the presence of an acid binder and if desired in
the presence of a diluent.
The compounds of the formula I may also be obtained by
reacting an imidazoline-2~4-dione of the ~ormula
O Rl
~ R2
XCC 12-S~N~,NH IV,
o
R1, R2 and X having the above meanings, with a sulfenyl chloride
of the formula IIIb, i~ desired in the presence of an acid binder
and if desired in the presence of a diluent.
The compounds of the formula I according to the invention
may further be obtained by reacting an N-cyclopropylimidazoline-
-2~4-dione of the ~ormula
O Rl
~ R2
D~Ny NH V,
b
with a sulfenyl chloride of the formula XCC12-S-Cl (IIIa) or
YCC12-S-Cl (IIIb), R1, R2, X and Y having the above meanings,
~9~(~S
O.Z. 0050/032590
with elimination of the cyclopropyl group as allyl chloride and
if desired in the presence of an acid binder and if desired in
the pre~ence o~ a diluent.
Finally, the compounds of the formula I according to the
inv~ntion in which X or X and Y denote fluorine m~y be obtained
by reacting an imidazoline-2 4-dione of ~he formula
O R
R2
Cl C-S- ~ ;S-CCl VI,
R1 and R2 having the above meanings, with anhydrous hydrofluoric
acid, in order to exchange one or two ~luorine atoms in the tri
chloromethylthio side chain ~or one or two chlorine atoms.
The first three of the abo~e reactions according to the in-
vention of imidazoline-2,4-diones of the ~ormul~e II, IV and V
are advantageously carried out in solvents or diluents inert to
the reactants~ e.g., toluene, xylen~, diethyl ether, tetrahydro-
~uran, dioxane, dimethoxyethane, acet~ne, methyl ethyl ketone,
ethyl acetate, methylene chloride, and chloro~orm.
The reaction with a compound o~ the formula VI can be carried
out in an excess o~ hydrofluoric acid as diluent.
Examples o~ suitable acid binders are inorganic bases such
as hydroxides or carbonates of alkali metals and alkaline earth
metals (e.g., NaOH, Na2C03), and particularly tertiary amines,
~uch as triethylamine, dimethylaniline, and p~ridine.
me reactions are carried out at, for instance, from -30
to ~100 C, pre~erably from -10 to+25C~ and at atmospheric
pre3~ure. The imidazoline-2,4-diones o~ the formulae II and IV
used as starting materials are known from the literature and
may be prepared in accordance with Bucherer ~J. Prakt. Chem.
140, 303, 1934) or Cremlyn (J. Chem. Soc. 6240, 1964)
_ 3 _
~9~
O.Z. 0050/0325~0
The first reaction described above, employing a compound
of the formula II, is preferred.
The compounds of the formula I according to the invention
are colorless crystalline products readily soluble in ethyl
- acetate, acetone, ethanol9 tetrahycLrofuran, methylene chloride,
chloroform, dimethyl sulfoxide, dimethyl~ormamide, and N-methyl-
pyrrolidone.
Individual examples of the new active ingredients are given
below (the imidazoline-2,4-diones are designated "hydant;oins"
in the following):
1,3-bis-(trichloromethylthio)-hydantoin
1,3-bis-(dichlorofluoromethylthio)-hydantoin
1-trichloromethylthio-3-dichlorofluoromethylthiohydantoin
1-dichlorofluoromethylthio-3-trichloromethylthiohydantoin
1,3-bis-(trichloromethylthio)-~-methylhydantoin
- 1,3-bis-(dichloro~luoromethylthio)-5-methylhydantoin
1~3-bis-(trichloromethylthio)-5,5-dimethylhydantoin
1,3-bis-(dichloro~luoromethylthio)-5,5 dimethylhydantoin
1~3-bis-(trichloromethylthio)-5-methyl-5-ethylhydantoin
1-dichlorofluoromethyl-3-trichloromethylthio-5-methyl-5-ethyl-
hydantoin
1,3-bis-~trichloromethylthio)-trans-cyclohexanespiro-5-hydantoin
1,3-bis-~dichlorofluoromethylthio)-trans-cyclohexanespiro-5-hydantoin.
The manufacture o~ the active ingredients is illustrated by
the following examples.
EXAMPLE 1
O~>~ ` ,
ClC13-S~ N~N-S-Cl~12F
At about 0 t;o ~5 C, 16.9 g (0~1 mole) of dichlorofluoro
methylsulfenyl chloride and subsequently 10.1 g (0.1 mole)o~ tri-
ethylamine are dripped, while stirring thoroughly, into a sus~
- 4 -
s
O.Z. 0050/032590
pension of 24.9 g (0.1 mole) of 3-trichloromethylthiohydantoin
in 200 ml of anhydrous ethyl acetate. After stirring for 2 hours
at room temperature (20 C) the precipitated triethylamine hydro-
chloride is filtered off and washed with 50 ml of ethyl acetate.
The filtrate is extracted by shaking with 250 ml of water, dried3
clarified with 1 g of animal charcoal, and concentrated. The
residue crystallizes at 0C after the addition of 50 ml of
n-pentane. There is obtained 31.3 g (82% of theory) of 1-dichloro-
fluoromethylthio-3-trichloromethylthiohydantoin; m.p.: 114-116C.
The 3-trichloromethylthiohydantoin (m.p.o 184C) used as
starting material was prepared in accordanGe with
R.J.W. Cremlyn (J. Chem. Soc., 6240, 1964).
EXAMPLE 2
O q~
y
O
a) At about 0C, 37.2 g (0.2 mole) of trichloromethylsulfenyl
chloride and subsequently 20.2 g (0.2 mole) of triethylamine are
dripped, while stirring thoroughly3 into a suspension of 10 g
(0.1 mole) of hydantoin in 150 ml of anhydrous ethyl acetate.
After stirring for 90 minutes at room temperature, the precipitated
triethylamine hydrochloride is filtered off and washed with
100 ml of ethyl acetate. The filtrate is concentrated and the
residue is crystallized by trituration with n-pentane. There is
obtained 36.1 g (~0.5% o~ theory) o~ 1,3-bis-(trichloromethyl-
thio)-hydantoin, mOp.: 142C.
b) At about 25C, 37.2 g (0.2 mole) of trichloromethylsul-
fenyl chloride and subsequently 20.2 g (0.2 mole) of triethylamine
are dripped, while stirring thoroughly, into a suspension of
14.0 g (0.1 mole)of 3-cyclopropylhydantoin in 150 ml of anhydrous
hydantoin. After stirring for 12 hours at room temperature, the
~.
os
O.Z. 0050/032590
precipitated triethylamine hydrochloride is filtered off and
the reaction mixture is worked up as in Example 1. There is
obtained 23.5 g (59% of theory) of 1,3-bis-(trichloromethyl-
thio)-hydantoin; m.p. 140 -142 C.
The 3-cyclopropylhydantoin (m.p.: 137-139C) used as starting
material was prepared in accordance with A. Mouneyrat (Chem. Ber.,
33, 2393, 1900) from cyclopropyl isocyanate and glycocoll.
The compounds in Table 1 below were prepared analogously:
TABLE 1
0 Rl
~R2
XCC12-S-N~N-S-CC12Y
Example No. R1 R X Y m.p.C
3 H H F F 92- 94
4 H H F Cl 132-133
H -CH3 C~ Cl 106-108
6 H -CH3 ~ F 87- 89
-CH3 -CH3 Cl Cl 114-116
8 -CH3 -CH3 F F 88- 89
9 -CH3 -C2H5 Cl Cl 110-112
-C~3 -C2H5 Cl F 97- 98
11 Cl Cl 14~ 9
12 -(CH2)5- F F 87- 88
The compounds according to the invention may be converted
into the usual ~ormulations, e.g. solutions~ emulsions, suso
penslons, dusts, powders, pastes and granules. The formulations
are prepared in conventional manner, e.g., by extending the
active ingredient with solvents and/or carriers 9 if desired
using emulsifiers and dispersants. Where water is used as diluent,
other organic solvents may also be employed as auxiliary sol-
- 6 -
O.Z. 0050/032590
vents. Suitable compounds ror preparing such formulations are
solvents such as aromatics (e.g., xylene, benzene), chlorinated
aromatics (e.g. chlorobenzenes), paraffins (e.g., petroleum
fractions), alcohols (e.g., methanol~ butanol), amines (e.g.,
ethanolamine, dimethylformamide), and water; carriers such as
natural rock flours (e.g., ~aolins, diatomaceous earth, talc,
chalk) and synthetic rock flours (e.g.~ highly disperse silicic
acid, silicate~); emulsifiers such as nonionic and anionic
emulsi~ying agents (e.g. polyoxyethylene-~atty alcohol ether
alkyl sulfonates and aryl su}fonates); and dispersants such a~
lignin, sulfite waste liquors and methyl cellulose.
Thè formulations generally contain from 0.1 to 95, and
pre~erably ~rom 0.5 to 90, wtZ of active ingredient.
The formulation~ and the ready-to-use products made there
from, e.g., solutions, emulsions, suspensions, powders, dusts,
pastes or granules, are applied in known manner, for example by
spraying, atomizing~ dusting, scattering, seed-disinfecting,
pouring, painting or impregnating.
me application rates depend on the ef~ect desired, and
range ~rom 0.01 to 3 kg of active ingredient per hectare, or mcre.
Some of the compounds also have a good bactericidal action on
bacteria such as Staphylococcus aureus. When the active ingre-
dients according to the invention are used to protect materials~
fungi such as Aspergillus-niger, Aspergillus flavus, A~pergillus
versicolor, Penicillium funiculosum, Chaetomium globosum,
Cladosporium herbarum, Pullularia pullulans, Humicola grisea,
and Sclerophoma pityophila are combated. When the active ingre-
dients are used to protect materials, e.g., as fungicides for
sur~ace coatings and soft PVC (polyvinyl chloride) ,the application rates are
fran 0.05 to 5~ (by weight) of active ingredient, based on the total
weight of the paints to be preserved or the PVC to be micro-
bicidally treated. The new active ingredients may also be used
-- 7 --
~., ' ~ ' ~ .
, . . .
05
O.Z. 0050~032590
as fungicidally ef~ective components of preservatives ~or
protecting wood against wood-discoloring fungi. Application
is e~ected by tre~ting, e.g., impregnating or painting, the
wood with these agents.
The agents according to the invention may also be mixed
and applied with other acti~e ingrQdients, e.g., herbicides,
insecticides, growth regulators, bactericides, fungicides and
fertilizers. When mixed with other fungicides, the spectrum of
fungicidal action is in many ca~es increased; with a number of
these fungicidal compositionsy synergistic ef~ects also occur;
i.e., the fungicidal action of the combination product is
greater than the effect of the individual components added
together.
Examples of fungicides which may be combined with the com~
pounds according to the invention are: dithiocarbamates and
their derivatives, e.g~ iron(III) dimethyldithiocarbamate, zinc
dimethyldithiocarbamate9 manganese N,N-ethylene-bis-dithiocarb-
amate, manganese zinc N,N-ethylenediamine-bis-dithiocarbamate,
zinc N,N-ethylene-bis-dithiocarbamate, tetramethylthiuram di-
sul~ide, the ammonia complex o~ zinc N,N-ethylene-bis-dithio-
carbam~te and N,N'-polyethylene- bis (thiocarbamoyl)-disulfide,
zinc N,N'-propylene-bis-dithiocarbamate, and the ammonia complex
of zinc N,N'-propylene-bis-dithioc~rbamate and N-Nt-polypropylene-
-bis-(thiocarbamoyl)-disul~ide; nitro derivatives, e.g. dinitro-
-(1-methylheptyl)-phenyl crotonate, 2-sec.-butyl-4,6-dinitro-
phenyl 3,3-dimethylacrylate and 2-sec.-butyl-4,6-dinitrophenyl
isopropyl carbonate; heterocyclic compounds, e.g. N-trichloro-
methylthiotetrahydrophthalimide, N-trichloromethylthio-pnthal-
imide, 2-heptadecyl-2-imidazoline acetate, 294-dichloro-6-(o
-chloroanilino~-s-triazine, 0,0-diethyl phthalimidophosphono-
thioate, 5-amino-1-(bis-(dimethylamino)-phosphinyl)-3-phenyl-
-1,2~4-triazole, 5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole,
- 8 -
iO5
O.Z. 0050/032590
2,~-dicyano-1,4~dithiaanthraquinone, 2-thio-1,3-dithio(4,5-b)-
quinoxaline, methyl 1-(butylcarbamoyl)-2-benzimidazole-carbamate,
2-methoxycarbonylamino-benzimidazol~, 2-thiocyanatomethylthio-
-benzthia~ole, 4-(2-chlorophenylhydrazono)-3-methyl-5-i~oxazolone,
pyridine-2-thio-1-oxide, 8-hydroxyquinoline and its copper
salts,, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-
-dioxide, 2,3-dihydro-5~carboxaniliclo-6-methyl-1,4-oxathiine,
2-fur-2-yl-benzimidazole, piperazine-1,4-diyl-bis-(1-(2,2,2-tri-
chloroethyl)-formamide) 9 2-thiazol-4-yl-benzimidazole, 5 butyl-
-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis-(p-chloro-
phenyl)-3-pyridinemethanol, 1,2-bis-(3-ethoxycarbonyl-2 thio-
ureido)-benzene, 1,2-bis-(3-methoxycarbonyl-2-thioureido)-ben-
zene and various fungicides~ e.g. dodecylguanidine acetate,
3-~2-(3,5-dimethyl-2-hydroxycyclohexyl)-2-hydroxyethy].)-glutar-
imide, hexachlorobenzene, N-dichlorofluoromethylthio-N',N'-di-
methyl-N-phenyl-sulfuric acid diamide, 2,5-dimethyl-furan-3-
-carboxylic acid anilide, 2~5-dimethylfuran-~-carboxylic acid
cyclohexylamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic
acid anilide, 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-tri-
chloroethane, 2,6-dimethyl-N-tridecyl-morpholine and its salts,
and 2,6-dimethyl-N-cyclododecyl-morpholine and its salts.
In the following experiment~ demon~trating the fungicidal
action of the compounds according to the invention, the following
prior art active ingredients were used for comparison purposes.
1,3-bis-(trichloromethylthio)-5-ethyl-5-phenylhydantoin
(comparative compound A)
1,3-bis-(trichloromethylthio)-5,5-diphenylhydantoin
(comparative compound B).
~ 9 _
, . . . .
O.Z. 0050/032590
E.YAMPLE 13
Plasmopara viticola in grapes
LeaYes of potted vines o~ the ~I~ller-Thurgau variety are
sprayed with aqueous dispersions containing ~dry basis) 80~ (wt%)
of the active ingredient and 20~ of sodium lignin sulfonate.
0.1, 0.05 and 0.025~ (dry basis) spray liquors are used. After
the spra~ed-on liquor has dried, tXe leaves are infected with a
zoospore suspension o~ Plasmopara viticola. The plants are
~irst placed for 16 hours in a steam-saturated (moist)chamber
at 20C, and then in a greenhouse for 8 day~ at from 20 to
30C. To accelerate and intensify the sporangicphore discharge,
the plants are then again placed in the moist chamber ~or
16 hours. The spore sites on the underside of the lea~es are
then counted; 0 denotes no ~ungus attack, graduated down to 5,
which denotes total attack (control).
Active Leaf attack after spraying with liquor con-
ingredient taining active ingredients in amounts of
0.1% 0.05% 0.025g
. . ~
1 0 2 2
3 0 0 2
4 0 0 0
0 0 0
6 0 0 0
8 0 0 0
g 0 2 2
0 0 2
12 0
Control tuntreated~ 5
.. ....
~ . ... _
-- 10 --
~9605
O.Z. 0050/032590
EXA~LE 14
Phytophthora infestans in tomatoes
Leaves of tomatoes of the "GroRe Fleischtomate" variety are
sprayed with aqueous dispersions containing (dry basis) 80% (wt%)
of active ingredient and 20% of soditlm lignin sulfonate. 0.1%
(dry basis) spray liquors are used. After the sprayed-on layer
has dried, the leaves are infected with a zoospore suspension
of Phytophthora infestansO The plants are then placed for 5 days
in a steam-saturated (moist) chamber kept at 16C. After this
period, the disease has spread on the untreated control plants
to such an extent that from 80 to 100~ of the leaf surface is
covered.
Active Leaf attack after spraying with liquor con-
in~redient taining 0.1% of active ingredient
0
3 0
4 0
0
7 0
9
12 0
A (prior art) 2
B (prior art) 2
Control (untreated) 4
. .
O = no ~ungus atta~k, graduated down to 5 = total attack
EXAMPLE 15
Botrytis cinerea in pimientos
Pimiento seedl.ings of the "Neusiedler ldeal Elite" variety
with 4 to 5 well developed leaves were sprayed to runaff with
0.1% (wt~) aqueous spray liquors containing (dry basis) 80% of
active ingredient and 20% of sodium lignin sulfonate~ After the
60~
O.Z. 0050/032590
sprayed-on layer had dried, the plants were sprayed with a
conidial suspension o~ the fungus Botrytis clnerea and placed,
at 22 to 24C, in a high-humidity chamber to obtain optimum
conditions for fungus growth. After 5 days, the disease had
spread on the untreated plants to such an extent that the
necroses covered most of the leaf surface.
Active ingredient Leaf necroses a~ter spraying
with 0.1% l'iquor
~ _ .
0
7 o
9 2
o
A (prior art) 5
B (prior art) 5
Control (untreated) 5
. . _
0 = no necroses, graduated down to 5 = 2/3 of lea~ ~urface
covered with necroses
EXAk~LE 16
Septoria nodorum in wheat
Leaves of pot-grown wheat plants of the l'Jubilar" variety
are sprayed to runoff with aqueous liquors containing 0.2 and
0.1% (wt%) of active ingredient in emulsi~ied ~orm. After the
sprayed-on layer ha~ dried, the plants are sprayed with a spore
suspension of the ~ungus Septoria nodorum and placed, at 16 to
18C, in a high-humidity chamber to obtain optimum conditions
for fungus growth. After 14 days, the disease has spread on the
untreated control plants to such an extent that the lea~ blotches
cover m st o~ the lea~ surface.
3o
- ~2 -
~ s
O.Z~ 0050/032590
Active ingredient Leaf attack a~ter spraying with liquor
containing active ingredient in amounts of
0.2% 0.1%
- 1
2 3.5 3.5
3 2 2
~ 2 2
1 2
7 1 2
8 _ 2.5
2 3.5
11 2.5 3.5
12 - 2.5
A (prior art) 5.5 5.5
B (prior art) 4~5 4
Control (untreated) 5.5
,
0 = no blotches, graduated down to 7 - more than 2/3 of leaf surface
covered with blotches
EXAMPLE 17
Pythium spec. in pea seedling~
Pea seeds of the "Senator'l variety are ehoroughly dusted
with a disin~ectant formulation containing, in triturated ~orm,
40~ (wt%) of active ingredient and 60~ of talc, in amounts of
O.3 g per 100 g of seed. The seeds treated in this manner are ~; -
placed, in pots, in 30il heavily infected with Pythium. After
21 days, the dam2ge c~used by the disease is compared with that
on the untreated control plan~s.
- 13 -
O~
O.Z. 0050/032590
Active ingredient Percentages of diseased pea plants
(21 day~ after emergence)
0
3 25
8 0
A (prior art) 85
B (prior art) 90
Control (untreated) 90
EX~MPLE 18
Aspergillus niger
The active ingredients are added to a nutrient solution
ideally 3uited for promoting the growth of the fungus Aspergillus
niger, in amounts of 100, 50, 25 and 10 parts by weight per million
parts of nutrient solution. 20 ml lots of the nutrient soluti~n
treated in thi manner are placed in 100 ml glass fla~ks and in~
oculated with 0.3 mg of Aspergillus spores. The flasks are incubated
at 36 C for 120 hour~ and the extent of fungus spread - pre-
dominantly on the surface of the nutrient solutions - is then asse~sed.
C = no fungus growth, graduated down to ~:
5 = uncontrolled ~ungus growth (surface of nutrient solution
completely covered by fungus~
Active ingredientAmount of active ingredient in
nutrient so.ution in ppm
100 50 25 10
2 0 0 0 0
4 0 0 2 5 : :
6 0 0 0 4
8 0 0 0 4
0 0 0 0
12 0 0 0 2
A (prior art) 5 5 5 5
B (prior art) 5 5 5 5
Control (un~reated) 5
- 14 -
05
O.Z. 0050/032590
EXAMPLE 19
90 parts by weight of compound 1 is mixed with 10 parts by
weight of N-methyl-~-pyrrolidone. A mixture is obtained which is
suitable ~or application in the form of very fine drops.
EXAMPLE 20
20 parts by weight of compound 2 is dissolved in a mixture
consisting of 80 parts by weight of xylene, 10 parts by weight
of the adduct of 8 to 10 moles o~ ethylene oxide to 1 mole of
oleic acid-N-monoethanolamide, 5 parts by weight of the calcium
salt of dodecylbenzene~ulfonic acid, and 5 parts by weight of
the adduct of 40 moles of ethylene oxide to 1 mole of castor
oil. By pouring the solution into 100,000 parts by weight of
water and uniformly distributing it therein, an aqueous dis-
persion is obtained containing 0.02~ by weight of the active
ingredient.
EX~PLE 21
20 parts by weight of compound 3 is dissol~ed in a mix-
ture consisting of 40 parts by weight of cyclohexanone,
30 parts by weight of isobutanol, 20 parts by weight of the
adduct of 7 moles of ethylene oxide to 1 mole of isooctyl-
phenolg and 10 parts by weight of the adduct of 40 moles o~
ethylene oxide to 1 mole of castor oil. By pouring the solution
into 100,000 parts by weight of water and finely distributing
it therein, an aqueous di~persion i obtained containing 0.02%
by weight of the ac.tive ingredient.
EXAMPLE 22
20 parts by weight of compound 4 is dissolved in a mix-
ture consisting of 25 parts by weight of cyclohexanol, 65 parts
by weight of a mine~ral oil fraction having a boiling point
between 210 and 280C, ~nd 10 parts by weight of the adduct of
40 moles of ethylene oxide to 1 mole of castor oil. By pouring
the solution into 100,000 parts by weight o~ water and uniformly
- 15 -
g~ii(35
O.Z. 0050/032590
distributing it therein, an aqueous di~persion is obtained
containing 0.02~ by weight of the active ingredient.
EXAMPLE 23
20 parts by weight of compound 5 is well mixed with
3 parts by weight o~ the sodium salt of diisobutylnaphthalene-
-~-sulfonic acid, 17 parts by weight of the sodium salt of a
lignin-sulfonic acid obtained from a sulfite waste liquor,
and 60 parts by weight of powdered silica gel, and triturated
in a hammer mill. By uniformly distributing the mixture in
20,000 parts by weight of water, a spray liquor is obtained
containing 0.1% by weight o~ the active ingredient.
EXAMPLE 24
3 parts by weight o~ compound 6 is intimately mixed with
97 parts by weight of particulate kaolin. A dust is obtained
containing 3% by weight o~ the active ingredient.
EXAMPLE 25
30 parts by waight of compound 7 is intimat~ly mixed
with a mixture consisting of 92 parts by weight of powdered
silica gel and ~ parts by weight of paraffin oil which has
been sprayed onto the surface o~ this silica gelO A formulation
of the active ingredient is obtained having good adherence.
EXAMPLE 26
40 parts by weight o~ compound 1 is intimately mixed with
10 parts of the sodium salt of a phenolsulfonic acid-urea-form-
aldehyde condensate, 2 parts of silica gel and 48 parts of
water. Dilution in 100,000 parts by weight of water gives an
aqueous dispersion containing 0.04 wt~ of active ingredient.
- 16 -
g~o~
O.Z. 0050/032590
EXAMPLE 27
20 parts of compound 2 is intima.tely mixed with 2 parts
of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of
a fatty alcohol polyglycol ether, 2 parts of the sodium salt
of a phenolsulfonic acid-urea-formaldehyde condensate and
68 parts of a paraffinic mineral oil. A stable oily dispersion
is obtained.
!
. - 17 -
