Note: Descriptions are shown in the official language in which they were submitted.
.
133~ 38~ ~
- 1 - o.z. 0050/39507
3-substituted pyridlnes and fungicides containing them
The present invention relates to nove~ 3-
substituted pyridine derivatives and fungicides ~hich
conta;n these compounds, and ~ethods for controlling
fungi.
Structurally related 3-propenylpyridines, eg. 2-
n-butyl-3-(4-methylphenyl)-1-(3-pyridyl)-2-propen-1-ol,
Z-n-butyl-3-(4-~ethylphenyl)-1-(3-pyridyl)-2-propen-1-one
and 2-n-butyl-3-(4-fluorophenyl)~ 3-pyridyl)-2-propen-
1-ol are disc~osed as fungicides in EP-214 566. Ho~ever,
their action is not al~ays conpletely satisfactory for
certain indications, particularly at lo~ application
rates.
~e have found that 3-substituted pyrid;ne der;va- A~,
tives of the fornula
OR1
~R: (I)
1~ R2
I~n
~here R1 is hydrogen, C1-Cg-alkyl~ C3-Cg-alkeny~ C3-
Cg-alkynyl, C2-C12-acyl, C2-C12-haloacyl or unsaturated
-; C3-acyl, or is benzoyl uhich is unsubstituted or ~onosub- ~ -
stituted to trisubstituted by C1-C4-alkyl, C1-C4-alkoxy,
phenyl, acetoxy, C1-C4-haloalkyl, halogen or nitro, or is
benzyl uhich is unsubst;tuted or subst;tuted by 1 to 3
radica~s of the tYPe C1-C4-alkyl, C1-C4-alkoxy, C1-
C4-haloalkyl, halogen, cyano or n;tro, R2 ;s hydrogen,
~;~ 25 C1-C12-alkyl, C3-C12-cycloalkyl, C4-C20-cycloalkyl-
alkyl, C4-C20-alkylcycloalkyl, unsubst;tuted or subst;tu-
ted C7-C20-arylal,ky~,~oir lun~subst;tuted or subst;tuted!C7-
C20-aryloxyalkyl ~hose aryl radicals are unsubstituted or
- ~onosubstituted to trisubstituted by C1-C4-alkyl, C1-C4-
30 aikoxy, C1-C4-haloalkyl or halogen, R3 ;s a rad;cal ~
R~ R5 RS ~-- ~ :
~R O r ~R 5
~? ~N~R~
: 133~.~8~
,
- 2 - O.z. 0050/39507
where R4 to R~ independently of one another are each hydro-
gen, C1-C4-alkyl, Cl-C4-alkoxy, C1-C4-haloalkyl,
C2-C4-alkoxycarbonyl, C2-C4-dialkylamino, phenyl, hydro~-
yl or halogen, and R4 and R5 or RS and R6 together may
S furthermore be the group -CH=CH-CH=CH-, and n is 0 or 1,
and their plant-tolerated salts surprisingly have a sub-
stantially better fungicidal action than the unsaturated
pyridine derivatives disslosed in EP-214 566.
R1 jS, for example, hydrogen, methyl, ethyl, n-
propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-
pentyl, isopentyl, n-hexyl, neohexyl, n-heptyl, n-octyl,
2,4,4-trimethylpent-2-yl, 2-ethylhexyl, allyl, 2-methyl-
allyl, 3-methylallyl, 3,3-dimethylallyl, 3-buten-1-yl, 3-
octen-1-yl, propargyl, 3-octyn-1-yl, acetyl, mono-, di-
or trichloroacetyl, trifluoroacetyl, propionyl, 3-bromo-
propionyl, butyryl, 4-bromobutyryl, 3-methylbutyryl, 3,3-
dimethylbutyryl, pentanoyl, hexanoyl, heptanoyl, octan-
oyL, 2-ethylhexanoyl, nonanoyl, decanoyl, lauroyl, dodecan-
oyl, acryloyl, benzoyl, mono-, di- or trimethylbenzoyl,
4-tert-butylbenzoyl, 4-phenylbenzoyl, fluorobenzoyl, mono-,
di- or trichlorobenzoyl, trifluoromethylbenzoyl, mono-,
di- or trimethoxybenzoyl, 2-acetoxybenzoyl, mono- or di-
~ nitrobenzoyl, benzyl, mono-, di- or trimethylben2yl, 4-
- tert-butylbenzyl, mono-, di- or tr;methoxybenzyl, tri-
fluoromethylbenzyl, trichloromethylbenzyl, mono-, di- or
trichlorobenzyl, cyanobenzyl or mono- or dinitrobenzyl.
R2 j5, for example, hydrogen, methyl, ethyl, n-
propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-
pentyl, isopentyl, neopentyl, n-hexyl, neohexy~, n-
heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl,
cyclopentyl, cyc~ohexy~, cycloocty~, cyc~ododecy~, 2-
cyclohexylethyl, 3-cyclohexyl-2-methylproPyl, 4-tert-
butylcyclohexyl, benzyl, mono-, di- or trimethylbenzyl,
4-tert-butylbenzyl, mono-, di- or trimethoxybenzyl, tri-
fluoromethylbenzyl, mono-, di- or trichlorobenzyl,
fluorobenzyl, phenylethyl, (4-fluorophenyl)-ethyl,
(chlorophenyl)-ethyl, (2,4-dichlorophenyl)-ethyl,
.
133i3~
- 3 - o.z. 0050/39507
phenylpropyl, 4-tert-butylphenylpropyl, 3-phenyl-2-
propyl, 3-(4-tert-butylphenyl)-2-propyl, 3-(chloro-
phenyl)-2-propyl, 3-(fluorophenyl)-2-propyl, 3-(2,4-di-
chlorophenyl)-2-propyl, phenoxymethyl, mono-, di- or tri-
chlorophenoxymethyl, fluorophenoxymethyl, phenoxyethyl,
mono-, d;- or trichlorophenoxyethyl, fluoroPhenoxyethyl, ;
phenoxypropyl, mono-, di- or trichlorophenoxyproPyl,
,luorophenoxypropyl, phenoxybutyl, mono-, di- or tri-
chlorophenoxybutyl, mono-, di- or trichlorophenoxybutyL
- 10 or fluorophenoxybutyl.
R3 ;s, for example, phenyl, mono-, di- or tri-
~ethylphenyl, ethylphenyl, 4-tert-butylphenyl, ~ono-, di-
or trimetho~yphenyl, trifluoromethylphenyl, trichloro-
~ethylphenyl, N,N-dimethyl(ethyl)aminophenyl, methoxy-
carbonylphenyl, hydroxyphenyl, biphenyl, mono-, di- or
trichlorophenyl, fluorophenyl, naphthyl, pyridyl, methyl-
pyridyl, chloropyridyl, quinolyl or iso~uinolyl.
Plant-tolerated salts are, for example, addition
salts with inorganic mineral acids, such as hydrochlor-
ides, hydrobromides, sulfates, phosphates or nitrates;
salts with formic acid or ~ith alkylcarboxylic acids,
such as acetates, 2-ethylhexanoates or oxalates; and
salts with arylsulfonic acids, such as benzenesulfonates,
toluenesulfonates or dodecylbenzenesulfonates.
The compounds of the formula I may have two centers
of asymmetry and therefore occur in two diastereomeric
forms, which, if required, can be separated by known
~ethods. The present invention relates to the individual
diastereom-rs as well as their mixtures. ~
The compounds of the formula I may be in the form ~r
of the pyridines,or in the form of the pyridine N-oxides.
The novel 3-substituted pyridines of the formula
I can be prepared, for example, by reacting a pyridyl
atcohol of the formula I
OH
C~R3 t I )
,
~ ~33~ 3~5
- 4 - O.Z. 0050/39507
~here R2 and R3 have the abovementioned meanings, ~ith
an alkyLating or acylating agent of the formula II
R1-X (II)
~here R1 has the abovementioned meanings, excePt for
hydrogen, and X is a nucleofugic group, eg. chlorine,
bromine, iodine, methanesu~fonate, benzenesulfonate or
p-toluenesulfonate.
This reaction is advantageously carried out by
a procedure in which a mi~ture of pyridyl alcohol of
the formula I, not less than an e~uimolar amount of an
auxiliary base and an inert, organic solvent, such as
diethyl ether, tetrahydrofuran, dioxane, dimethylformam-
ide, Jimethyl sulfoxide, acetonitrile, toluene or xylene,
is initially taken and the alkylating or acylating agent
is metered in.
The reaction temperatures are from 0 to 120C,
preferably from 20 to 80C.
Suitable auxiliary bases are inorganic and or-
ganic acid acceptors.
Examples of inorganic bases are sodium hydride,
sodium amide, sodium hydroxide, sodium carbonate, potas- ~ -
sium carbonate and potassium hydroxid~.
Examples of organic bases are amines, in particu-
lar tertiary amines, such as triethylamine, ethyldiiso-
25 propy~amin- or pyridine, and alcoholates, such as sodium -;
methy~at-, sodium ethylate or potassium tert-butylate.
In an advantageous variant of this process, the
reactions of the pyridyl alcohols of the formula I with
alkylating agents,of the formula II are carried out
in a tvo-phase system consisting of aqueous sodium
hydroxide solution and an organic solvent, preferabLy ;~-
toluene or dichloro~ethane, ~ith the addition of a phase-
-~` transfer cata~yst, eg. tetra-n-butylammoniu~ chLoride,
~- benzy~triethylammonium chloride or methyltrioctylammonium
chloride.
r
- , 133138~
The novel compounds I where R1 ;5 hydrogen are
prepared, for example, by reducing a pyridyl ketone ot
the formula III or a pyridyl alcohol of the formula IV
H
~R3 ( 111 ) G~R~ ~ IY?
S where RZ and R3 have the abovementioned meanings, with a
reducing agent, for exampla a complex hydride or hydro-
gen, in the presence of a catalyst (cf. for e~a~ple M
Hudlicky, Reductions in Organic Che~istry, page 119 et
seq , Ellis Horwood Serie~, Chichester, 19a4) The pre-
paration of the pyridy~ ketones of the for~ula III and ofthe pyridyl alcohol~ of the formula IV i~ kno~n ~EP-A-214
566)
In another process for the preparation of th~
novel co~pounds I ~here R1 j5 hydrog~n, for ~xanple, an
organometallic conpound of tht for~ula V
R~ ~ ~
2 :
where R2 and R3 have th~ abovt~entioned meanings and M
is lithiu~ or th- radical ~gCl or Mg~r, is react~d ~ith
nicotinaldehyde ~3-tornylpyridine) For this purpose,
the organo~etallic co~pound of th~ fornula V i~ advan-
-~ t~g~ou~ly initially taken in an inert solv~nt, prefer-
ably diethyl eth~r or tetrahydrofuran, and th~ nicotin-
ld~hyd~ ettred ;n ~ a ~ixture ~ith tht ~n~ solvent -~
at tro~ -30 to ~50C.
The organonetallic compound~ of the formula V are ~-
obtainable fro~ th~ corresponding halidts ~chloride~ or
bro~ides) by kno~n proces~t~ tcf. for exanple Houben-
~eyl, Methoden der Organi~chen Chenie, Volumt 13/1, page
134 t ~eq., Georg Thie~e Vtr~ag~ Stuttgart 1970; ibid.,
Voluoe 13/2a, pagt 54 ~t se~., G~org Thie~ V~r~ag, Stutt-
gart, 1973). Tht ~atttr ar~ ~ith~r kno~n or can be ~
,:
, . . ,, , .. , , , . .," ,., . . ;,. ..
.
- 6 - o.z. 0050/39507
prepared by known processes. The Pyridine N-oxides are ;
obtained from the pyridines by known processes, for e~a~-
ple ~y oxidation with a peracid (cf. for exa~Ple Katrit-
zky and Lagowski, Che~istry of Heterocyclic N-O~ides,
pages 21-56, Acade~ic Press, Ne~ York, 1971).
The Examples ~hich follow illustrate the prepara-
tion of the novel fungicidal pyridines.
EXAMPLE 1
2-n-butyl 3-(4-fluorophenyl)-1-(3-pyridyl)-propan-1-ol
1û In a 0.3 l stirred autoclave, a mixture of 17.1 9
(0.6 mole) of 2-n-butyl-3-(4-fluorophenyl)-1-(3-pyridyl)-
2-propen-1-ol, 160 ml of tetrahydrofuran and 4.5 9 of a
hydrogenation catalyst (O.SZ of Pd on Al203) is hydro-
genated at 30C and under a hydrogen pressure of 50 bar
until the pressure remains constant. The solution is
then filtered under suction over silica gel, the filtrate
is evaporated down under reduced pressure and the residue
is purified by distillation. Yield: 7.9 9 of conpound
No. 1, bp. 187C (0.3 mbar).
'
EXAMPLE 2
2-n-butyl-3-(4-fluorophenyl~-1-(3-pyridyl)-propan-1-ol 2,4-
dichlorobenzoate
4.6 9 ~0.02Z ~ole) of 2,4-dichlorobenzoyl chlor- ;~
ide, dissolved in 10 nl of dichloromethane, are added
dropuis~ to a ~olution of 5.74 9 (0.02 ~ole) of con-
pound No. 1 in S0 ~l of dichloronethane and 10 ~l of tri-
ethyla~ino at roon te~perature. The ~ixture is stirred
overnight, aft~r which 30 ~l of 10X strength NaHC03
solution are add~d and st~ir~ring is continued for a
further hour. The organic phase is washed with ~ater,
- dried over ~gS~4 and evaporated down under reduced
pressure. The residue is purified by chro~atograPhy over
- silica gel using a 9 : 1 dichloronethane/acetone ~i~ture
as the nobile phase. 6.7 9 (73~ of theory) of co~pound
No. 2 are obtained as a yellow oil.
F' - : - . . ..
1331385
- 7 - O.Z. 0050/39507
~XAMPLE 3
2-n-butyl-3-(4-fluoroPhenyl)-1-(3-pyridyl)-propan-1-ol 4-
chlorobenzy! ether
0.72 9 (0.03 mole) of sodium hydride is added to
a solution of 5.74 9 (0.02 mole) of compound 1 in 20 ml
of dimethylformamide, and the mixture is stirred at
50C until the evolution of hydrogen has ended. The
mixture is cooled to room temperature, after which 4.0 9
(0.025 mole) of 4-chlorobenzyl chloride in 10 ml of di- -
methylformamide are added dropwise sufficiently slowly to
prevent the internal temperature from exceeding 40C.
Stirring is continued for 1 hour at room temperature
(20C), 50 l of water are carefully added drop~ise at
0C and 100 ml of ether are introduced. The aqueous
phase is separated off and extracted by shaking with
ether. The combined organic phases are dried over
MgS04 and evaporated down under reduced pressure. The
residue is purified by chromatography over silica gel
using a 9 : 1 dichloromethane/acetone mixture as the
mobile phase. 6.7 9 (81X of theory) of co~pound No. 3
are obtained as a yellow oil.
EXAMPLE 4
3-t4-fluorophenyl)-1-(3-pyridyl)-propan-1-ol
A solution of 10.7 9 (0.10 mole) of nicotinalde-
hyde in 100 ml of diethyl ether i5 added dropwise, while
stirring, to a solution prepared from 2.92 9 ~0.12 mole)
of magn-sium and 24.4 9 ~0.12 mole) of 2-~4-fluoro-
phenyl)-ethyl bromide in Z50 ~l of diethyl ether, and the
mixture is then refluxed for 2 hours. Cooling is
followed by hydrolysis ~ith water, and the pH is brought
to 8 with saturat,ed,aqueous! NH4Cl solution. The phases
are separated, the aqueous phase is extracted twice more
with ether, and the combined organic phases are washed ~--
with water and dried over MgS04. The solvent is
3S evaporated off and the residue is distilled under reduced ~;
pressure to give 10.2 9 ~44X of theory) of compound No. 4
of boiling point 190C ~2 mbar).
1331385
- 8 - O.Z. 0050/39507
The following compounds are obtained in a corre-
sponding manner.
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r . ~
' ~" ' . , ~ .:
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: ',,: ,
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a~ -- ._ .o ~ a~
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O C C_ ~ e
C O ~ C C C C O O ~ ~ C OL L
----Cc--~Co~L----__~,cccooCccoo
O O O O -- I O S ~ ~ C O C C -- O O O C r o O O '
OOOOC~O--C~COCC--OOO~ OOO----
~~ E ~ u ~ E ~ ~ ~ C c t:L ~ u u ~ ~ u u ~ ~ ~ ` ~
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O ~ ~ S ~ S S ~ ~ '
S _ _ _ S _ _ ~ _ S _ CL ~L -- _ _ -- C
C C C~ ~ ~ ~ V ~ ~ ~ L ~ ~ ~ ~ ~ e C LO
C S O S S S O S S ~ S O S ~ ~ S _ S S - O
o O s o o O s o o ~ o s o I I o c -- o o C
L L ~ L L L ~ L L . L ~ L ~ ~ L ~ ~ . L L U
~_ _ _ _ _ _ O ~ _ ~ O ~ ~ _ S~ -- ~
S S I C S S I S _ ~ S I _ ~ ~ .C ~ C ~> C C S I
t.> v ~ ~ ~ ~ ~ E ~ u
C C C C C N 1~ N 1~
a~ ~ ~ c ~ c e c c c
S ~, _ C _ ~C~ _ $ g ~ ~ ~ ~
O -- O -- O ~ O ~`~ O ~ O O O O O O O _ _ -- --
L :~, L ::~ o o o o~ o o o o o o o _ o " ,, ~ o o o o .
:~ _ ~ _ ~ _ ~ _ ~ _ CL _ -- _ _ C S S ~ ~ ~ L L L L '-
v v ~ ~ n ~ c~
o I o I ~O~ i 0~. 1 OX ~ ~ ~ I ,~. ~ c c c I ~ I C C C C .
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-- S ---- I S -- -- I I -- -- ~ ~ ~ I S -- ~
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C~ ~ 8 ~ CL-- 1~ n ~ ~ 8 0 ~ ` E
L ~, . 2 L U L 2 ~ I _ o o s o I L X ' ~
O S ~1 ~ O O _ O ~ _ O O _ O ~ ,C O o ~_ o _ ~ ~ C
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CL L ~ L L L L
L LL II I I I I ~, ~, ~ , ~ C C C C ~C C ~ C
O O O O O O C C ,C C ,C C C ~ ~> ~ ~ ~ ~ ~ ~>
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O -- I o ~ o c o o o o c o o c o s o o O C O O O C
L ~ ~ ~ L ~ ~ L ~ ~ L ~
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14 O.Z. 0050/3~ ~ 3 ~. 3 8 ~
In general terms, the novel compounds are extremely effective on a broad
spectrum of phytopathogenic fungi, in particular those from the class
consisting of the Ascomycetes and Basidiomy~etes. Some of them have a
systemic action and can be used as foliar and soil fungicides.
The fungicidal compounds are of particular interest for controlling a
large number of fungi in various crops or their seeds, especially wheat,
rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee,
sugar cane, fruit and ornamentals in horticulture and viticulture, and in
10 vegetables such as cucumbers, beans and cucurbits.
The novel compounds are particularly useful for controlling the following
plant diseases:
15 Erysiphe graminis in cereals,
Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,
PodoSphaera leucotricha in apples,
Uncinula necator in vines,
Puccinia species in cereals,
20 Rhizoctonia solani in cotton,
Ustilago species in cereals and sugar cane,
Venturia inaequalis (scab) in apples,
Helminthosporium species in cereals,
Septoria nodorum in wheat,
25 Botrytis cinerea ~gray mold) in strawberries and grapes,
Cercospora arachidicola in groundnuts,
Pseudocercosporella herpotrichoides in wheat and barley,
Pyricularia oryzae in rice,
Phytophthora infestans in potatoes and tomatoes,
30 Fusarium and Verticillium species in various plants,
PlaSmopara viticola in grapes,
Alternaria species in fruit and vegetables.
The compounds are applied by spraying or dusting the plants with the
35 active ingredients, or treating the seeds of the plants with the active
ingredients. They may be applied before or after infection of the plants
or seeds by the fungi.
The novel substances can be converted into conventional formulations such
40 as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
The application forms depend entirely on the purposes for which they are
intended; they should at all events ensure a fine and uniform distribution
of the active ingredient. The formulations are produced in known manner,
for example by extending the active ingredient with solvents and/or
carriers, with or without the use of emulsifiers and dispersants; if water
133~.38~
O.z 0050/39507
is used as solvent, it is also possible to employ other organic solvents
as auxiliary solvents. Suitable auxiliaries for this purpose are solvents
such as aromatics (e.g., xylene), chlorinated aromatics (e.g., chloro-
benzenes), paraffins (e.g., crude oil fractions), alcohols (e.g.,
5 methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g.,
ethanolamine, dimethylformamide), and water; carriers such as ground
natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground
synthetic minerals (e.g., highly disperse silica and silicates);
emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethyl-
10 ene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); anddispersants such as lignin, sulfite waste liquors and methylcellulose.
The fungicides generally contain from G.1 to 95, and preferably from 0.5
to 90, wt% of active ingredient. The application rates are from 0.02 to 3
15 kg or more of active ingredient per hectare, depending on the type of
effect desired. The novel compounds may also be used for protecting
materials, e.g., on Paecilomyces variotii.
The agents and the ready-to-use formulations prepared from them, such as
20 solutions, emulsions, suspensions, powders, dusts, pastes and granules,
are applied in conventional manner, for example by spraying, atomizing,
dusting, scattering, dressing or watering.
Examples of formulations are given below.
I. 90 parts by weight of compound no. 1 is mixed with 10 parts by weight
of N-methyl-a-pyrrolidone. A mixture is obtained which is suitable for
application in the form of very fine drops.
30 II. 20 parts by weight of compound no. 5 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 of ethylene oxide and 1 mole of oleic acid-N-
monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-
sulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene
35 oxide and 1 mole of castor oil. By pouring the solution into water and
uniformly distributing it therein, an aqueous dispersion is obtained.
III. 20 parts by weight of compound no. 6 is dissolved in a mixture con-
sisting of 40 parts by weight of cyclohexanone, 30 parts by weight of iso-
40 butanol, 20 parts by weight of the adduct of 40 moles of ethylene oxideand 1 mole of castor oil. By pouring the solution into water and finely
distributing it therein, an aqueous dispersion is obtained.
1331385
16 o z 0050/39507
IV. 20 parts by weight of compound no. 1 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 and 1 mole
5 of castor oil. By pouring the solution into water and uniformly distribut-
ing it therein, an aqueous dispersion is obtained.
V. 80 parts by weight of compound no. 1 is well mixed with 3 parts by
weight of the sodium salt of diisobutylnaphthalene-a-sulfonic acid,
10 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained
from a sulfite waste liquor, and 7 parts by weight of powdered silica gel,
and triturated in a hammer mill. By uniformly distributing the mixture in
water, a spray liquor is obtained.
15 Vl. 3 parts by weight of compound no. 5 is intimately mixed with 97 parts
by weight of particulate kaolin. A dust is obtained containing 3% by
weight of the active ingredient.
VII. 30 parts by weight of compound no. 6 is intimately mixed with a
20 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.
25 VIII. 40 parts by weight of compound no. 1 is intimately mixed with
10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde
condensate, 2 parts of silica gel and 48 parts of water to give a stabte
- aqueous dispersion. Dilution in water gives an aqueous dispersion.
30 IX. 20 parts by weight of compound no. 1 is intimatety mixed with 2 parts
by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by
- weight of a fatty alcohol polyglycol ether, 2 parts by weight of the
sodiùm salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68
parts by weight of a paraffinic mineral oil. A stable oily dispersion is
35 obtained. ; ~ , ! ' '
."
In these apptication forms, the agents according to the invention may also
be present together with other active ingredients, for example herbicides,
insecticides, growth regulators, and fungicides, and may furthermore be
40 mixed and applied together with fertilizers. Admixture with other fun-
gicides frequently results in a greater fungicidal action spectrum.
~ 133~ 385
17 O.Z. 0050/39507
The following list of fungicides with which the novel compounds may be
combined is intended.to illustrate possible combinations but not to impose
any restrictions.
5 Examples of fungicides which may be combined with the novel compounds are:
sulfur, ::
dithiocarbamates and their derivatives, such as
ferric dimethyldithiocarbamate,
10 zinc dimethyldithiocarbamate,
zinc ethylenebisdithiocarbamate,
manganese ethylenebisdithiocarbamate,
manganese zinc ethylenediaminebisdithiocarbamate, : .
tetramethylthiuram disulfides,
15 ammonia complex of zinc N,N'-ethylenebisdithiocarbamate,
ammonia complex of zinc N,N'-propylenebisdithiocarbamate,
zinc N,N'-propylenebisdithioccarbamate and
N,N'-polypropylenebis(thiocirbamyl) disulfide;
20 nitro derivatives, such as
dinitro(1-methylheptyl)-phenyl crotonate,
2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,
2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and
~` diisopropyl 5-nitroisophthalate;
.~ 25
heterocyclic substances, such as
2-heptadecylimidazol-2-yl acetate,
~: 2,4-dichloro-6-(o-chloroanilino)-s-triazine,
~: a, 0-diethyl phthalimidophosphonothioate,
30 5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole,
2,3-dicyano-1,4-dithioanthraquinone,
2-thio-1,3-dithio[4,5-b]quinoxaline,
methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate,
2-methoxycarbonylaminobenzimidazole,
35 2-(fur-2-ylj-benzimidazole,
2-(thiazol-4-yl)benzimidazole,
N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide, , '~
N-trichloromethylthiotetrahydrophthalimide,
-~ N-trichloromethylthiophthalimide, ~.
: ~- 40
N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfuric acid diamide, ~ -
5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,
- 2-thiocyanatomethylthiobenzothiazole,
;~ 1,4-dichloro-2,5-dimethoxybenzene,
~ ,
, , ., ., , ~ , ~ ~ , .. . .
18 0 z. 0050/39507 1 33~. 385
4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,
2-thiopyridine l-oxide,
8-hydroxyquinoline and its copper salt,
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne,
5 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiyne 4,4-dioxide,
2-methyl-5,6-dihydro-4H-pyran-3-carboxanilide,
2-methylfuran-3-carboxanilide,
2,5-dimethylfuran-3-carboxanilide,
2,4,5-trimethylfuran-3-carboxanilide,
10 2,5-dimethyl-N-cyclohexylfuran-3-carboxamide,
N-cyclohexyl-N-methoxy-2,5-diethylfuran-3-carboxamide,
2-methylbenzanilide,
2-iodobenzanilide,
N-formyl-N-morpholine-2,2,2-trichloroethylacetal,
15 piperazine-1,4-diylbis-(1-(2,2,2-trichtoroethyl)-formamide),
1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane,
2,6-dimethyl-N-tridecylmorpholine and its salts,
2,6-dimethyl-N-cyclododecylmorpholine and its salts,
N-t3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,
20 N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-piperidine,
1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-lH-1,2,4-
-triazole,
1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-lH-1,2,4-
-triazole,
25 N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N -imidazolyl-urea, :
1-(4-chlorophenoxy)-3~3-dimethyl-1-(lH-1~2~4-triazol-1-yl)-butan-2-one~
1-(4-chlorophenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)-butan-2-ol,
1-(4-phenylphenoxy)-3,3-dimethyl-1-(lH-1,2,4-triazol-1-yl)-2-butanol,
~-(2-chlorophenyl)-~-(4-chlorophenyl)-5-pyrimidinemethanol,
30 5-butyl-(2-dimethylamino-4-hydroxy-6-methylpyrimidine,
bis-(p-chlorophenyl)-3-pyr~dinemethanol,
1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene,
1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene,
and various fungicides, such as
35 dodecylguanidine acetate,
3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]-glutaramide, ~:
hexachlorobenzene, . -:
DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alanate, ~
methyl DL-N-(2,6-dimethylphenyl)-N-(2 -methoxyacetyl)-alanate, :
40 N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyrolactone, `
methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)-alanate,
5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,
3-[3,5-dichlorophenyl]-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,
3-(3,5-dichlorophenyl)-1-isopropylcarbamylhydantoin,
~,. . .... . . ........ ... .... ..... .
,-
--\
1331385
19 O.Z. 0050/39507
N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,
2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]-aCetamide,
1-[2-(2,4-dichlorophenyl)-pentyl]-lH-1,2,4-triazole,
2,4-difluoro-a-(lH-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol,
5 N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-
chloro-2-aminopyridine, and
1-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-lH-1,2,4-triazole.
Use examples
The agents used for comparison purposes were
2-n-butyl-3-(4-methylphenyl)-1-(3-pyridinyl)-2-propen-1-one (C),
2-n-butyl-3-(4-fluorophenyl)-1-(3-pyridinyl)-2-propen-1-ol (A), and
2-n-butyl-3-(4-methylphenyl)-1-(3-pyridinyl)-2-propen-1-ol (B)
15 disclosed in EP-214,566.
Use Exampte 1
Action on wheat mildew
20 Leaves of pot-grown wheat seedlings of the "FrUhgold" variety were sprayed
with aqueous liquors containing (dry basis) 80% of active ingredient and
20% of emulsifier, and dusted, 24 hours after the sprayed-on layer had
dried, with spores of wheat mildew (Erysiphe graminis var. tritici). The
plants were then set up in the greenhouse at from 20 to 22C and a rela-
25 tive humidity of from 75 to 80%. The extent of mildew spread was assessedafter 7 days.
The results show that active ingredients 1 and 5, when employed as 0.025
and 0.006wt~ spray liquors, had a better fungicidal action (97%) than ;
30 prior art active ingredients A, B and C (70%).
use Example 2
Action on cucumber mildew
35 Leaves of pot-grown cucumber seédlings of the i'Chinesische Schlange"
variety were sprayed at the two-leaf stage with an aqueous conidial
suspension of cucumber mildew. After about 20 hours, these plants were
sprayed to runoff with aqueous liquors containing (dry basis) 80% of
active ingredient and 20% of emulsifier. After ~he sprayed-on layer had
40 dried, the plants were set up in the greenhouse at 20 to 22C and a
- relative humidity of 70 to 80%. The extent of fungus spread was determined
21 days after inoculation.
- -~ 1331385
O.Z. 0050/39507
The results show that active ingredients 1, 5 and 6, when emplayed as
0.0125 and 0.006wt% spray liquors, had a better fungicidal action (90%)
than prior art active ingredients A and B (10~o).
5 Use Example 3
Action on Plasmopara viticola
Leaves of potted vines of the M~ller-Thurgau variety were sprayed with
aqueous suspensions containing (dry basis) ôO% of active ingredient and
10 20% of emulsifier. To assess the duration of action, the plants were set
up, after the sprayed-on layer had dried, for 8 days in the greenhouse.
Then the leaves were infected with a zoospore suspensio~ of Plasmopara
viticola. The plants were first placed for 48 hours in a water vapor-
saturated chamber at 24C and then in a greenhouse for 5 days at from 20
15 to 30C. To accelerate and intensify the sporangiophore discharge, the
plants were then again placed in the moist chamber for 16 hours. The
extent of fungus attack was then assessed on the undersides of the leaves.
The results show that active ingredients 1, 5 and 6, when applied as
20 0.05wt% spray liquors, had a better fungicidal action (97%) than prior art
comparative agents A, B and C (S0%).
use Example 4
Action on Pyrenophora teres
Barley seedlings of the "Igri" variety were sprayed to runoff at the
2-leaf stage with aqueous suspensions containing (dry basis) 8~ of active
ingredient and 20~ emulsifier. After 24 hours the plants were inoculated
with a spore suspension of the fungus Pyrenophora teres and placed for 48
30 hours in a high-hum1dity climatic cabinet kept at 18C. The plants were
then cultivated for a further 5 days in the greenhouse at 20-22C and a -~
relative humidity of 70%. The extent of fungus spread was then determined.
The results show that active ingredients 1, 5 and 6, when applied as 0.05%
35 spray liquors, had a better fungiicidal action (97%) than~prior art active
ingredients A, B and C (50%).
'
' ~,
~ `
