Note: Descriptions are shown in the official language in which they were submitted.
2~
o,z. ooso/033880
FUNGICIDE CONTAINING A 3-CYCLOHEXANE-1-~MINOPROPANE DERIVATIVE,
ITS MANUFACTURE, AND ITS USE FOR COMBATIN~t FUNGI
The present invention relates to a fungicide for crop protection
containing the trans compound, or a salt thereof, of a 3-~p-tert-
-butylcyclohexyl)-2-methylpropane compound to which is attached,
in the 1-position, the nitrogen atom of a nitrogenous heterocycle.
It has been disclosed (German Laid-Open Application `
DR-OS 2,752,135) that 3-(4'-tert-butylcyclohexyl-1')-2-methyl-1-
-piperidinopropanes and salts thereof may be used to combat plant-
-pathogenic fungi.
The said compounds are, with respect to the two substituents
in the 1- and 4-positions on the cyclohexane ring, in the form of
cis-trans isomer mixtures.
We have found that trans compounds of the formula
CH3 A 3
CH -C ~ CH2-CX-CH2-R
CH7
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where R denotes the radical of a saturated~ 5-, 6- or 7-membered
nitrogenous heterocyclic radical which is attached at the nitrogen,
is unsubstituted or mono- or polysubstituted by methyl, and may
bear, in the 4-position to the nitrogen atom , an oxygen atom or
a C=0 radical instead of the methylene radical, and salts thereof,
have a better fungicidal action than the corresponding cis compound.
It is surprising that the trans compounds have a fungicidal action
on rusts (Puccinia species) in, inter alia, cereals and beans which
is from 10 to 100 times greater than that of the corresponding
cis compounds. By trans compound, we mean not only the pure trans
compound but also mixtures containing more than 50% (wt~) of the
trans compound. Examples of the radical R are the radicals of
piperidine, hexamethylenimine, 3~5-dimethyl-4-piperidone and
2,6-dimethylmorpholine. Examples o~ salts are those with hydrohalic
acids, e.g., hydrochloric and hydrobromic acid, or salts with
sulfuric acid, acetic acid and p-toluenesulfonic acid.
The trans compounds are obtained in salt ~orm when the cis-
-trans mixture obtained on hydrogenation of the corresponding
1,4-disubstituted phenyl compound to the cyclohexane compound is,
a~ter distilling off the solvent used ~or the hydrogenation,
enriched to a trans fraction of more than 85~ by fractional
distillation in a 10- to 100-tray column (reflux ratio from 1:1
to 1:100 and pressure of from 0.05 to 50 mm at top of column), and
the pure trans isomer is reacted with a strong acid to give an
addition salt which is then allowed to crystallize out in an
organic solvent.
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O.Z. 0050/033880
Manufacturing processes
1. Manufacture of cis- and trans-3-(4-tert-butylcyclohe~yl-1)-2-
-methyl-1-(3~-methyl-1-piperidino)-propane.
- a) Synthesis of the aromatic amine
306 g of 3-(p-tert-butylphenyl)-2-methylpropanal is introduced
into a 2-liter, 3-necked flask, and 72.5 g of 98~ (wt~) strength
formic acid is dripped in. O~er a period of 3 hours, 149 g of
3-methylpiperidine is then added dropwise, the temperature rising
from 25 to over 50C. The reaction mixture is subsequently refluxed
for 12 hours, whereupon C02 is evolved.
Upon completion of the reaction, the mixture is subjected to
fractional distillation. After first runnings of 47 g, which distil
over at 130C/0.2 mm, 3-(p-tert-butylphenyl)-2-methyl-1-(3'-methyl-
-1'-piperidino)-propane distils over at from 130 to 133C/0.2 mm.
A total of 355 g is obtained, which is equivalent to a yield,
based on the aldehyde used, of 82.4~.
b) Hydrogenation to the cyclohexane derivative
309 g of 3-(p-tert-butylphenyl)-2-methyl-1-(3'-methyl~
-piperidino)-propane is hydrogenated in 1,000 g of dioxane with
the aid of 0.5 g of Ru203 hydrate in a ~-liter rotating autoclave.
At a hydrogen pressure of 100 bars and a temperature of 120C,
no more hydrogen is absorbed a~ter 3 hours. Subsequently at 140C
and 120 bars hydrogen pressure, a pressure drop of 35 bars over
12 hours is recorded; after readjustment of the hydrogen pressure
: to 160 bars and at 160C, another pressure drop of 10 bars is
registered over a period of 10 hours. No more hydrogen is absorbed
when the hydrogen pressure is reset to 160 bars and the temperature
raiseà to 180C.
c) Fractional distillation
3 The reaction mixture, 1,310 g, is subjected to fractional
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distillation at 10 mbars in a column containing 10 sieve trays.
After the dioxane has been distilled off, the following fractions
are obtained at a reflux ratio of 1:5:
1. up to 185C - 27 g, 85g of which is cis and 10% of which is
trans compound (remainder of 5% is first runnings);
2. at 185C - 114 g, 75% of which is cis and 25% of which is
trans compound;
3. up to 186C - 60 gg 40% of which is cis and 60% of which is
trans compound;
5. up to 187C - 55 g, 30~ of which is cis and 70% of which is
trans compound.
The distillation residue (40 g) is subjected to molecular
distillation at 10 mbars and 187C. There is obtained 38 g, 92%
of which is trans and only 8% cis. 2 g of distillation residue
remains.
The cis:trans ratio is determined by gas chromatography.
504 g of 3-(4~-tert-butylcyclohexyl-1~)-2-methyl-1-(3~-methyl-
-1'-piperidino)-propane produced by the method described above
and which contains a total of 425 g of cyclohexane derivative
(54g cis and 46~ trans) is rractionated in a column having 20 sieve
trays. The reflux ratio i5 adjusted to 1:3.
~ Up to a temperature of 192C, 70 g of first runnings distil
over. Thereafter, the following fractions are obtained:
1. up to 197C~28 mbars - 13 g, 85% of which is cis and 3% of
which is trans (remainder of 12% is first runnings);
2. up to 198C/26mbars - 52 g, 93~ of which is cis and 7% of
which is trans;
3. up to 197 C/25 mbars - 87 g, 90% of which is cis and 10~ of
which is trans;
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4. up to 192CJ22 mbars - 82 g, 85~ of which is cis and 15
of which is trans;
5. up to 196C~22 mbar~ - 81 g, 80% of which is cis and 20%
of which is trans;
6. up to 202C/28 mbars - 87 g, 30% of which is cis and 70%
of which is trans;
7. up to 196C/22 mbars - 73 g, 97% of which is trans and 3%
of which is cis.
The distillation residue-(27 g) is subjected to molecular
distillation. There is obtained 24 g, 98~ of which is trans com-
pound.
The initial and/or final fractions are further purified to
the pure cis form by recrystallization of the hydrobromide in
acetic acid/water and to the brans compound with the aid of hydrogen
chloride in methanol.
d) Manufacture of the HBr salt of the pure cis ~orm
20 g of aqueous 48~ strength hydrobromic acid is added to
25 g of the first fraction obtained above. 50 g of acetic acid is
then added and all the crystalline product is dissolved by heating.
Upon cooling, the hydrobromide of the cis form crystallizes out.
NMR analysis confirms that it is the pure cis form. There is
obtained 28 g of melting point 210C.
C H N Br
calc.: 64.15~ 10.77% 3.74% 20~34~o
found: 64.5% 10.3~ 3.60% 20.6~
e) Manufacture of the HCl salt of the pure trans form
60 g of hydrogen chloride is added to 35 g of fraction 5,
obtained above, in metAanol. Upon cooling, 28 g of hydrochloride
having a melting point of 168C crystallizes out. NMR analysis
3 confirms the trans form.
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o.z. 0050/033880
2. Manufacture of cis- and trans-3-(4'-tert-butylcyclohexyl-1')-2-
-methyl-1-t 3~, 5'-dimethyl-1'-piperidino)-propane
a) 361 g of 3-(p-tert-butylphenyl)-2-methylpropanal is reacted,
as described in Manufacting Process 1, with 200 g of 3,5-dimethyl-
piperidine and 86 g of 98% strength formic acid. The amine is
purified by fractional distillation in a 10-tray column at a
pressure of 0.2 mbar. 406 g of pure amine distils over at 136C.
b) Hydrogenation to the cyclohexane compound
80 g of dioxane is added to 70 g of 3- (p-tert-butylphenyl)-
-2-methyl-1-(3',5'-dimethyl-1'-piperidino)-propane in a shaker
autoclave having a reaction volume of 250 ml. 0.5 g of ruthenium
oxide hydrate is added as hydrogenation catalyst. At 120C, the
pressure is kept at 100 bars hydrogen by topping up over a period
of 37 hours with 358 bars.
Fractional distillation of the reaction mixture (139 g) gives
64 g of the cyclohexane derivative, which distils over between
136 and 146C/3 mm. Gas chromatographic analysis shows an isomer
mixture of the cis and trans forms o~ the cyclohexane derivative.
c) Fractional distillation
562 g of the aromatic amine which was hydrogenated in 1,000 g
of dioxane with the aid of Ru203.hydrate at a hydrogen pressure
of 140 bars and at 120C over a period of 20 hours is separated
as described in Manufacturing Process 1 in a column with 10 sieve
trays, the reflux ratio being 1:5.
The more than 90% cis cyclohexane derivative distils over at
124-125C/0.1 mm. The trans cyclohexane derivative tenriched to
more than 90% trans) distils over at 129-131C.
A repeat of the fractional distillation at 12-13 mm in a column
80 cm long and packed with silver wire coils gives 154 g of cis
3 compound enriched to more than 90%. A mid-fraction of 1~6 g was
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a 1:1 mixture of cis and trans cyclohexane derivative. The yield
of trans-enriched cyclohexane derivative (more than 90~ enrichment)
is 98 g.
The mid-fraction is again fractionated. Only a very small
amount of residue was formed - on fractional distillation of the
cis-trans isomer mixture (390 g) only 2 g of high boilers is
formed. At a pressure of 12 mm, the cis derivative distils over
a~ 193-195C and the enriched trans product at 199-200C.
d) Crystallization of the pure cis compound via the HCl salt
20 g of the cis product enriched to m~re than 90% is taken
up in 25 g o~ methanolic hydrogen chloride solution, whereupon
the solution heats up to almost boiling. Upon cooling, 12 g of
hydrochloride cr~stallizes out (active ingredient 19). The melting
point o~ the recrystallized cis cyclohexane derivative is 240C.
A sample of the salt decomposed with KOH revealed on gas chromato-
graphic analysis that the compound is trans-free cis.
e) Crystallization of the pure trans compound via the HCl salt
20 g of the trans product enriched to more than 90% is taken
up in 30 g of ethanolic hydrogen chloride solution. Upon cooling,
13 ~ of the hydrochloride of the pure trans compound (m.p.: 202C)
arystallizes out tactive ingredient 20). The free base, obtained
by decomposing a sample of the salt, re~eals on gas chromatographic
analysis that the compound is cis-free trans. NMR analysis con-
firms the gas chromatography findings.
3. Manufacture of cis- and trans-3-(4'-tert-butylcyclohexyl-1')-
-2-methyl-1-~2',6l-cis-dimethylmorpholyl)-propane
a~ 3-(p-tert-butylphenyl)-2-methyl-1-(2',6'-cis-dimethylmorpholyl)-
-propane is manufactured as described in Manufacturing Process 1
by reaction of 3~(p-tert-butylphenyl)-2-methylpropanal with 2,6-
3 -cis-dimethylmorpholine and formic acid. The aromatic amine is
llZZ~2~:
purified by distillation (it distils over at 170-175C/3.Ombars.
b) Hydrogenation to the cyclohexane compound
500 g of dioxane is added to 720 g of the morpholine derivative
described above. 0.5 g of ruthenium oxide hydrate is added as
hydrogenation catalyst. Hydrogenation is carried out in a 2.6 liter
rotating autoclave at a hydrogen pressure of 120 bars and a tem-
perature of 140C. Over a period of 24 hours, a total of 130 bars
of hydrogen is pressured in.
c) Fractional distillation
623 K Of the cis-trans isomer mixture (60% cis, 40% trans)
obtained is fractionated at a pressure of 3.0 mbars in an 80 cm
column packed with silver wire coils. The reflux ratio is set at
1:5. The cis compound distils over at 144-145C/3.0 mm. The cis
compound in the firs~ 3 fractions, each of about 70 g, was
enriched to more than 90%. The last 3 fractions (71 g, 54 g and
38 g) contain the enriched (more than 85~) trans compound.
d) Crystallization of the pure cis and trans HC1 salt
The pure hydrochloride of the cis compound may be obtained
by the method described in Manufacturing Processes 1 and 2, with
ethanolic hydrogen chloride solution; m.p.: 161C (active
ingredient 23~.
The pure trans compound forms a hydrochloride having a
melting point Of 199C (active ingredient 24),
Gas chromatogl~aphic analysis of the 2 free bases prepared from
the 2 salts by reaction with KOH reveals that the bases are pure.
The cis cyclohexane derivative thus prepurified contains less than
0.5g Qf trans product; the trans compound contains less than 1%
of cis compound. NMR analysis confirms the gas chromatography
findings.
3 The remaining active ingredients are prepared in the same way.
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,,
`` 112~S22
Active R b.p./m.p. C.
ingredient
no.
1 pyrrolidine cis base b-P16 177
pyrrolidine trans basè b-p4 = 130
3 pyrrolidine cis HCl salt m.p. = 170
4 pyrrolidine trans HCl salt m.p. - 208
piperidine cis base b Plo 180
6 piperidine trans base b.p3 = 135
7 4-methylpiperidine cis base b-P20= 2o5-2o6
8 4-methylpi.peridine trans base b.p3 ~ 146-147
9 hexamethylenimine cis base b Po,2 151
hexamethylenimine . trans base b Po,2 153
11 3,5-dimethyl-4- cis base b.p3 = 144
-piperidone
12 3,5-dimethyl-4- trans base b p ~148
-piperidone
13 4-ethylpiperidine cis base b.p3 = 157
14 4-ethylpiperldine trans base b.p4 ~ 159
4-ethylpiperidine cis HCl salt m.p. = 214
16 4-ethylpiperidine trans HCl salt m.p. = 240
17 3,5-dimethylpiperidine cis base b P18' 195
18 3,5-dimethylpiperidine trans base b P18 199
19 3,5-dimethylpiperidine cis HCl salt m.p. ~ 240 :
3,5-dimethylpiperidine trans HCl salt ;m.p. = 202
21 cis-2,6-dimethyl- cis base b.p3 - 145
morpholine
22 cis-2,6-dimethyl- trans base b.p3 D 148 :~
morpholine -
23 cis-2,6-dimethyl- cis HCl salt m.p. ~ 161 -
morpholine
24 cis-2,6-dimethyl- trans HCl salt m.p. = 199
dimethylmorpholine
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O.Z. 0050/033880
The fungicides are particularly suitable for combating plant
diseases, e.g., Erysiphe graminis in cereals, Erysiphe cichoriacearum
in Cucurbitaceae, Podosphaera leucotricha in apples, Uncinula
necator in grapes, Erysiphe polygoni in beans, Sphaerotheca pannosa
in roses, Microsphaera querci in oaks, Botrytis cinerea in straw-
berries and grapes, Micosphaerella musicola in bananas, Puccinia
species in cereals, Uromyces appendiculatus and U. phaseoli in
beans, Hemileia vastatrix in coffee, and Rhizoctonia solani. The
active ingredients have a systemic action; they are taken up not
only through the roots but also via the foliage, and translocated
in the plant ti~sue.
When the new active ingredients are used to treat plants against
fungus infections, application rates are from 0.025 to 5 kg of
active ingredient per hectare. For the surface protection of trees
or fruit, the active ingredients may also be used in conàunction
with plastics dispersions in amounts of from 0.25 to 5%, based on
the weight of the dispersion.
The fungicides generally contain from 0.1 to 95, and prèfer-
ably from 0.5 to 90, wt% o~ acti~e ingredient.
The active ingredients may also be mixed with other, prior
art, ~ungicides. In many cases, the spectrum of fungicidal action
is increased; with a number of these fungicidal compositions in
the weight ratio range of from 1:10 to 10:1, synergistic effects
also occur, i.e., the ~ungicidal action of the combination product
is greater than the effect of the individual components added
together.
Examples of fungicides which may ~e combined with the com-
pounds according to the invention are: dithiocarbamates and their
derivatives, e.g.~ zinc dimethyldithiocarbamate, manganese
3 N,N-ethylene-bis-dithiocarbamate, manganese zinc N,N-ethylenediamine-
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O.Z. 0050/033880
-bis-dithiocarbamate, zinc N,N-ethylene-bis dithiocarbamate,
tetramethylthiuram disulfide, the ammonia complex of zinc N,N-
-ethylene-bis-dithiocarbamate and N,N'-polyethylene-bis-(thio-
carbamoyl)-disulfide, zinc N,N'-propylene-bis-dithiocarbamate,
and the ammonia complex of zinc N,N'-propylene-bis-dithiocarbamate
and N,Nt-polypropylene-bis-(thiocarbamoyl)-disulfide; heterocyclic
compounds, e.g. N-trichloromethylthiotetrahydrophthalimide,
N-trichloromethylthio-phthalimide, N-(1,1,2,2-tetrachloroethylthio)-
-tetrahydrophthalimide, methyl 1-(butyl-carbamoyl)-2-benzimidazole
carbamate, 2-methyloxycarbonylamino-benzimidazole, 2,3-dihydro-5-
-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide, 2,3-dihydro-5-
-carboxanilino-6-methyl-1,4-oxathiine, 5-butyl-2-dimethylamino-4-
-hydroxy-6-methyl-pyrimidine, 1,2-bis-(3-ethoxycarbonyl-2-thio-
ureido)-benzene, 1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene
and various other fungicides, e.g., dodecylguanidine acetate,
N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenyl-sulfuric acid
diamide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,5-di-
methylfuran-3-carboxylic acid cyclohexylamide, 2,5-dimethylfuran-
-3-carboxylic acid-N-methoxy-cyclohexylamide, 2-bromo-benzoic acid
anilide, 2-iodo-benzoic acid anilide, diisopropyl 3-nitroiso-
phthalate, 1-(1,2,4-triazol-1'-yl-~1-(4'-chlorophenoxy)]-3,3-di-
methylbutan-2-one, 1-(1,2,4-triazol-1'-yl)-[1-(4'-chlorophenoxy)~-
-3,3-dimethylbutan-2-ol, 1-(1-imidazolyl)-2-allyloxy-2-(2,4-di- -
chlorophenyl)-e~hane, piperazine-1,4-diyl-bis-1-(2,2,2-trichloro-
ethyl)-formamide, 2,4,5,6-tetrachloro-isophthalonitrile, ~nd
1,2-dimethyl-3,5-diphenyl-pyrazolinium methyl sulfate.
Application may be effected for instance in the form of
directly sprayable solutions, powders, suspensions, dispersions,
emulsions, oil dispersions, pastes, dusts, broadcasting agents,
3 or granules by spraying, atomizing, dusting, broadcasting or
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watering. The forms of application depend entirely on the purpose
for which the agents are being used; in any case they should
ensure as fine a distribution of the active ingredient as possible.
- For the preparation of solutions, emulsions, pastes and
oil dispersions to be sprayed direct, mineral oil fractions of
medium to high boiling point, such as kerosene or diesel oil,
further coal-tar oils, and oils of vegetable or animal origin,
aliphatic, cycli~ and aromatic hydrocarbons such as benzene,
toluene, xylene, paraffin, tetrahydronaphthalene, alkylated
naphthalenes and their derivatives such as methanol, ethanol,
propanol, butanol, chloroform, carbon tetrachloride, cyclo-
hexanol, cyclohexanone, chlorobenzene, isophorone, etc., and
strongly polar solvents such as di~ethylformamide, dimethyl-
sulfoxide, N methylpyrrolidone, water, etc. are sùitable.
Aqueous formulations may be prepared from emulsion con-
centrates, pastes, oil dispersions or wettable powders by
adding water. To prepare emulsions, pastes and oil dispersions
the ingredients as such or dissolved in an oil or solvent may be
homogenized in water by means of wetting or dispersing age~ts,
adherents or emulsifiers. Concentrates which are su~table for
dilution with water may be prepared from active ingredient,
wetting agent, adherent, emulsifying or dispersing agent and
possibly solvent or oil.
Examples of surfactants are: alkali metal, alkaline earth
metal and ammonium salts of ligninsulfonic acid, naphthalene-
sulfonic acids, phenolsulfonic acidsg alkylaryl sulfonates,
alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline
earth metal salts of dibutylnaphthalenesulfonic acid, lauryl
ether sulfate, fatty alcohol sulfates, alkali metal and alkaline
3 earth metal salts of fatty acids, salts of sul~ated hexadecanols,
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heptadecanols, and octadecanols, salts of sulfated fatty alco-
hol glycol ethers, condensation products of sulfonated naphtha-
lene and naphthalene derivatives with formaldehyde, condensation
products of naphthalene or naphthalenesulfonic acids with phenol
and formaldehyde, polyoxyethylene octylphenol ethers, ethoxyl-
ated isooctylphenol~ ethoxylated octylphenol and ethoxylated
nonylphenol, alkylphenol polyglycol ethers, tributylphenyl
polyglycol ethers, alkylaryl polyether alcohols, isotridecyl
alcohol, fatty alcohol ethylene oxide condensates, ethoxylated
castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxy-
propylene, lauryl alcohol polyglycol ether acetalg sorbitol
esters, lignin, sulfite waste liquors and methyl cellulose.
Powders, dusts and broadcasting agents may be prepared by
mixing or grinding the active ingredients with a solid carrier.
Granules, e.g., coated, impregnated or homogeneous gra-
nules, may be prepared by bonding the active ingredients to
solid carriers. Examples of solid carriers are mineral earths
such as silicic acid, silica gels, silicates, talc, kaolin~
Attaclay, limestone, lime, chalk, bole, loess, clay, dolomite,
diatomaceous earth, calcium sulfate, magnesium sulfate, mag-
nesium oxide, ground plastics, fertilizers such as ammonium -
sulfate, ammonium phosphate, ammonium nitrate, and ureas, and
vegetable products such as grain flours, bark meal, wood meal,
and nutshell meal, cellulosic powders, etc.
There may be added to the compositions or individual active
ingredients oils of various types, herbicides, fungicides,
nematocides, insecticides, bactericides, trace elements,
fertilizers, antifoams (e.g., silicones), growth regulators,
antidotes and other effective compounds.
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EXPERIMENT
Action on wheat mildew
Leaves of pot-grown wheat seedlings of the "Jubilar" variety
are sprayed with aqueous emulsions consisting of 80% (by weight)
of active ingredient and 20% of emulsifier, and dusted, after the
sprayed-on layer has dried, with spores of wheat mildew (Erysiphe
graminus var. tritici). The plants are then placed in a ~reenhouse
at 20 to 22C and 75 to 80% relative humidity. The extent of
mildew spread is determined after 10 days.
lO Active ingredient Leaf attack after spraying with
liquor containing active ingredient
in amounts Or
_ o.oo6% 0.003%_ 0.0015~ O.OQ07%
9 (cis ~orm) 0 2 3 3
10 (trans form) 0 0 0 0
23 (cis form) 0 2 2-3 2-3
24 (trans form) 0 0 0 0
~ontrol (untreated) 5
0 = no attack, graduated down to 5 = total attack
EXPERIMENT 2
Action on leaf rust of wheat
Leaves of pot-grown wheat plants are artificially infected
with spores of leaf rust (Puccinia recondita), and the plants are
placed for 48 hours in a steam-saturated chamber at from 20 to
25C. The plants are then sprayed with aqueous liquors containing,
as a solution or emulsion in the water, a mixture made up of 80
of active ingredient and 2Q% of sodium lignin sulfonate, and are
set up in a greenhouse at from 20 to 22C and 75 to 80% relative
humidity. The extent of fungus spread is assessed after 10 days.
3o
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O.Z. 0050/033880
Active Leaf attack aftar spraying with liquor con-
ingredient taining active ingredient in amaunts of
0.012% 0. oo6 %o . 003% o. 0015%
5 (cis form) 2-3 2-3 2-3 4
6 (trans form~ 0 0 0 3
11 (cis form) 2 2-3 4 4-5
12 (trans form) 0 0 0 2
21 (cis form) 2 3 3 4
22 (trans form) 0 0 0 0
23 (cis form) 3 5 5 5
10 ` 24 (trans form) 0 0 2
Control (untreated) 5
.
0 = no attack, graduated down to 5 - total attack
EXAMPLE
90 parts by weight of compound 10 is mixed with 10 parts by
weight of N-methyl-C~-pyrrolidone. A mixture is obtained which is
suitable for application in the form of very fine drops.
EXA~LE 2
20 parts by weight of compound 6 is dissolved in a mixture
consisting of 80 parts by weight of xylene, 10 parts by weight
o~ the adduct of 8 to 10 moles of ethylene oxide with 1 mole of
oleic acid-N-monoethanolamide, 5 parts by weight of the calcium
salt of dodecylbenzenesulfonic acid, and 5 parts by weight of
the adduct of 40 moles of ethylene oxide with 1 mole of castor
oil. By pouring the solution into 100,000 parts by weight of
water and uniformly distributing it therein, an aqueous dispersion
is obtained containing 0.02% by weight of the active ingredient.
EXAMPLE 3
20 parts by weight of compound 12 is dissolved in a mixture
consisting of 40 parts by weight of cyclohexanone3 30 parts by
3 weight of isobutanol, 20 parts by weight of the adduct of 7 moles
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O.Z. 0050/033880
of ethylene oxide with 1 mole of isooctylphenol, and 10 parts
by weight of the adduct of 40 moles of ethylene oxide with 1 mole
of castor oil. By pouring the solution into 100~000 parts by
weight of water and finely distributing it therein, an aqueous
dispersion is obtained containing 0.02% by weight of the active
ingredient.
EXAMPLE 4
20 parts by weight of compound 22 is dissolved in a mixture
consisting of 25 parts by weight of cyclohexanol, 65 parts by
weight of a mineral oil fraction having a boiling point between
210 and 280C, and 10 parts by weight of the adduct of 40 moles
of ethylene oxide with 1 mole of castor oil. By pouring the solution
into 100l000 parts by weight of water and uniformly distributing
it therein, an aqueous dispersion is obtained containing 0.02%
by weight of the active ingredient.
EXAMPLE 5
20 parts by weight ~f compound 6 is well mixed with 3 parts
by weight of the sodium salt o~ diisobutylnaphthalene-C~-sulfonic
acid, 17 parts by weight of the sodium salt of a lignin-sul~onic
2~ acid obtained from a sulrite waste liquor, and 60 parts by weight
of powdered silica gel, and triturated in a hammer mill. By uni-
formly distributing the mixture in 20,000 parts by weight of
water, a spray liquor is obtained containing 0.1~ by weight of
the active ingredient.
EXAMPLE
3 parts by weight of compound 12 is intimately mixed with
97 parts by weight of particulate kaolin. A dust is obtained
containing 3~ by weight of the active ingredient.
EXAMPLE 7
30 parts by weight of compound 22 is inti~ately mixed with
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o. z. ooso/033880
a mixture consisting of 92 parts by weight of powdered silica gel
and 8 parts by weight of paraffin oil which has been sprayed
onto the surface of this silica gel. A formulation of the active
ingredient is obtained having good adherence.
EXAMPLE 8
40 parts by weight of coMpound 6 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% of active ingredient.
EXA~PLE 9
20 parts of compound 4 is intimately mixed with 12 parts of
the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a
fatty alcohol polyglycol ethèr, 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 -
