Note: Descriptions are shown in the official language in which they were submitted.
~3;~8~
The present invention relates to new 1,2,4-triazole
derivatives, processes for the manufacture thereof, and their
use as fungicides.
It has been disclosed that t-butyl 2-(1',2',4'-
triazol-l'-yl)-2-phenylacetate has a fungicidal action (German
Laid-Open Application DE-OS 2,638,470). However, its action,
particularly on mildews and rusts, is unsatisactory. It is
therefore hardly suitable for use as a crop protection agent
for combating injurious fungi.
We have now found new compounds having a superior
herbicidal action. The object of the invention was to provide
new 1,2,4-triazol-1-yl compounds of the formula
R O-CH-CO-Y
~ ~ (I)
where
Rl denotes phenyl substituted by cyclohexyl, phenyl, 1 to 3
halogen atoms or alkyl of 1 to 4 carbon atoms, and
R3
Y denotes oR2 or N
\ R4
R2 denoting alkynyl of 3 to 15 carbon atoms,
R denoting hydrogen, alkyl of 1 to 20 carbon atoms,
alkenyl of 3 to 15 carbon atoms, phenyl or cyanoethyl, and
R4 denoting phenyl, benzyl or phenyl or benzyl substituted
by 1 or 2 halogen atoms, trifluoromethyl or alkyl of 1 to 4
carbon atoms, or alkenyl or alkynyl of 3 to 15 carbon carbon
atoms, phenylethyl, naphthyl or cyanoethyl,
and their plant-compatible salts and metal complexes.
- 1 -
3Z5~30
In formule I, R preferably denotes l-chlorobutyn-
2-yl-4, 3-chlorobutyn-1-yl-4, 1-chlorpentyn-2-yl-4, butyn-2-
yl-l, butyn-l-yl-3, butyn-1-yl-4, 3-methylbutyn-1-yl-3 and
l-ethynylcyclohexyl.
Exemples of salts tolerated by crop plants are
hydrochlorides, hydrobromides, sulfates, nitrates, phosphates,
oxalates and dodecylbenzene sulfonates.
Metal complexes are compounds of the formula
10~ R10-CH--CO-~ \ ~
Me ~ ~ ~ ) Zk IX,
where Rl and Y have the above meanings, Me denotes a metal
cation, e.g., of copper, zinc, thin, manganese, iron, cobalt
or nickel, Z denotes the anion of an inorganic acid, e.g.,
hydrochloric acid, sulfuric acid, nitric acid, phosphoric
acid, or hydrobromic acid, and k and m denote one of the
integers 1, 2, 3 and 4.
A further object of the invention is to provide a
process for the manufacture of 1,2,4-triazolyl compounds of
the formula I wherein
a) a compound of the formula
R2-C ~ II,
where R2 and Y have the~above meanings and Ll and L2 are
identical or different and are nucleophilically displaceable
leaving groups, is reacted with a compound of the formula
RlOH III,
113~
where Rl has the above meanings, or a salt thereof, and with
1,2,4-triazole, or a salt thereof, in the presence or absence
of a solvent or diluent and/or of an inorganic or organic
base and in the presence or absence of a reaction accelerator
at from O to ].80C, or
b) a compound of the formula
H ~
RlO-C-C-OM IV,
N
~
where Rl has the above meaning and M denotes hydrogen, one
equivalent of a metal cation or a substituted or unsubstituted
ammonium ion, is reacted with a compound of the formula
HY V,
where Y has the above meanings, after or ~ith simultaneous
addition of reagents suitable for derivatizing acids, in the
presence or absence of a solvent or diluent and/or of an
inorganic or organic base and in the presence or absence of
a reaction accelerator at from -20 to +180C, or
c) a compound of the formula V is reacted with a compound
of the formula
L3Y VI,
where Y has the above meanings and L3 is a nucleophilically
displaceable leaving group, in the presence or absence of a
solvent or diluent and/or an acid binder and in the presence
or absence of a reaction accelerator at from -20 to +180C,
or
1132580
d) a compound of the formula
H_C ~ O
L VII,
where Rl, Y and L2 have the above meanings, is reacted with
1,2,4-triazole in the presence or absence of a solvent or
diluent and/or an inorganic or organic base and in the presence
or absence of a reaction accelerator at from -20 to +180C
and/ if desired, the compounds obtained according to a) to d)
are converted into salts and metal complexes tolerated by
plants.
Examples of nucleophilically displaceable leaving
groups Ll and L2 mentioned in processes a) and d) are halogen,
such as chlorine, bromine and iodine; bisulfate; hydrogen
sulfonate; and unsubstituted or substituted alkylsulfonyloxy,
arylsulfonyloxy, alkylsulfate, phenoxy, phenylthio, oxonium,
sulfonium or ammonium radicals. Suitable inorganic or organic
bases which may if desired also be used as acid binders in
reaction a) are, for example, alkali metal and alkaline earth
metal hyd~oxides, such as sodium hydroxide, potassium hydroxide
and calcium hydroxide; alkali metal carbonates, such as
potassium and sodium carbonate; alkali metal hydrides, such
as sodium hydride; alkali metal and alkaline earth metal
alcoholates, such as sodium methylate, magnesium ethylate and
sodium isopropylate; tertiary amines, such as trimethylamine,
triethylamine, N,N-dimethylaniline, N,N-dimethylcyclohexylamine,
N-methylpiperidine and pyridine; and azoles, such as 1,2,4-
triazole and imidazole. However, other bases usually employed30
may also be used.
Examples of suitable salts of compounds of the
formulae III and salts of 1,2,4-triazol are their alkali metal,
1~L3Z5l30
alkaline earth metal, and substituted or unsubstituted
ammonium salts.
The preferred solvents or diluents include halo-
hydrocarbons, such as methylene chloride, chloroform, 1,2-
dichloroethane and chlorobenzene; aliphatic or aromatic
hydrocarbons, such as cyclohexane, petroleum ether, benzene,
toluene and xylenes; alcohols, such as methanol, ethanol,
isopropanol and n-butanol; esters, such as ethyl acetate;
amides, such as dimethylformamide; nitriles, such as
acetronitrile; sulfoxides, such as dimethylsulfoxide; ketones,
such as acetone and methyl ethyl ketone; ethers, such as
diethyl ether, tetrahydrofuran and dioxane, and mixtures of
the above. Advantageously, the solvent or diluent is used
in an amount of from 100 to 2,000 wt~, preferably from 100 to
1,000 wt~, based on starting materials II or III.
Preferred reaction accelerators are metal halides
such as sodium bromide and potassium iodide, crown ethers,
quaternary ammonium compounds, such as tetrabutylammonium
iodide, acids, or combinations of these compounds.
The process according to the invention is in general
carried out at from 40 to 150C, for from 1 to 60 hours, under
atmospheric or superatmospheric pressure, and continuously or
batchwise.
In carrying out the process according to the invention,
the amounts employed per mole of compound II are in general
from 0.5 to 2 moles of compound III and 1,2,4-triazole,
preferably from 0.9 to 1.3 moles of III and 1,2,4-triazole,
from 1 to 4 moles, preferably from 1.8 to 2.3 moles, of base,
and, if a reaction accelerator is used, from 0.01 to 0.1 mole
thereof.
In a preferred form of process a) according to the
invention, the starting materials III and 1,2,4-triazole are
1132~3V
mixed, in optional sequence, with a base and a diluent, the
starting material II, with or without a reaction accelerator,
is then added and the reaction is carried out at from 40
to 150C, for from 0.5 to 120, preferably from 1 to 60, hours.
To isolate the compounds according to the invention,
the diluent is, if desired, removed, and the residue is taken
up in a suitable solvent and washed with water to remove excess
base and unreacted starting materials of the formula III and
1,2,4-triazole. In general, the products remaining after
removal of the solvent do not require any further purification,
but if necessary they can be additionally purified by conven-
tional methods, such as recrystallization, extraction and
chromatography.
The following are - without restricting the invention
- to them - examples of conventional reagents suitable for
derivatizing acids for process b): proton or Lewis acids,
inorganic and organic acid halides, such as thionyl chloride,
phosphorus pentachloride and acetyl chloride; chlorocarbonic
acid esters, such as the ethyl, tert~butyl and benzyl esters;
anhydrides, such as ketene; diimides, such as N,N'-dicyclohexyl-
carbodiimide; and carbonyl or sulfonyl diazoles, such as
carbonyldiimidazole, carbonylditriazole, sulfonyldiimidazole
and sulfonylditriazole.
For process c), particularly suitable compounds
of the formula VI are those in which L3 is a nucleophilically
displaceable leaving group, such as halogen, e.g., chlorine,
bromine and iodine; substituted or unsubstituted alkyl- or
arylsulfonyloxy, such as mesyloxy, trifluoromethylsulfonyloxy,`
brosyloxy and tosyloxy; an alkyl sulfate, such as methyl
sulfate; and the diazo group.
Preferred solvents or diluents and acid binders
preferably used for processes b), c) and d) are those given
'3~
J~ --6--
1:~3ZS8~
for process a).
The reactions according to processes b), c) and d)
described in general terms and the isolation of the compounds
according to the invention are carried out in conventional
manner (cf. Houben-Weyl, 8, 508 et seq., and 653 et seq.,
Stuttgart, 1952, and 15, 2, Stuttgart, 1974).
The starting materials of the formula IV may be
produced by reaction of a compound of the formula
Ll
R2-C~ X,
L2 OM
where R2, Ll, L2 and M have the ahove meanlngs, with a hydroxy
compound of the formula
R OH III,
where Rl has the above meanings, or a salt thereof, and with
1,2,4-triazole or a salt thereof, in the presence or absence
of a diluent and/or an acid binder and in the presence or
absence of a reaction accelerator, at from O to 180C.
The starting materials of the formula VII may be
prepared by conventional methods~ e.g., by halogenation of the
corresponding aryl- or heteroaryloxyalkanoic acid derivatives
(c.f. German Laid-Open Application DE-OS 1,808,034).
The compounds of the formula I have one or more
chiral centers; pure isomers can be obtained from the mixtures,
obtained by synthesis, in accordance with prior art methods.
The pure isomers anZ also mixtures thereof may
be used.
The following examples illustrate the production
of the new compounds.
- 7 -
. ,,
113Z580
Manufacture of the starting materlals
a) 90 parts of a technical-grade sodium methylate
solution in methanol (30 parts of sodium methylate in 100
parts of solution) is added to 81.5 parts of 2,4-dichlorophenol
and 34.S parts of 1,2,4-triazote in 300 parts of ethanol and
after brief stirring 109 parts of dibromoacetic acid is
introduced. The mixture is refluxed for 14 hours, the solvent
is stripped off and the residue is dissolved in about 1,000
parts of water. While cooling, the pH is brought to 1 by
adding concentrated hydrochloric acid, and the precipitate
which has formed is filtered off and washed with isopropanol.
After drying, 121 parts of 2-(2',4'-dichlorophenoxy)-2-(1',
2',4'-triazol-1'-yl)-acetic acid, of melting point 211-213C
(with decomposition), is obtained.
b) 771 parts of 4-chlorophenol and 414 parts of 1,2,4-
triazole are added to 1,080 parts of a technical-grade sodium
methylate solution in methanol (30 parts of sodium methylate
in 100 parts of solution). After briefly stirring the mixturet
774 parts of dichloroacetic acid is run in, during which
addition the temperature rises to about 60C. The methanol is
then distilled off and isopropanol is run in at the same time
in such amount that the reaction mixture can be stirred without
difficulty. When the internal temperature has reached 80C,
boiling is continued for 10 hours, the solvent is then distilled
off, ice water is added and the mixture is acidified with
concentrated hydrochloric acid. The precipitate formed is
filtered off, washed with isopropanol and dried. 676 parts
(58~ of theory) of 2-(4'-chlorophenoxy)-2-(1',2',4'-triazol-
l'-yl)-acetic acid of melting point 205-207C (with decom-
position) is obtained.
1132580
Manufacture of the end products
EXAMPLE 1
25 parts of 2-(4'-chlorophenoxy)-2-(1',2',4'-
triazol-l'-yl)-acetic acid was introduced into 100 parts of
methylene chloride, and 0.5 part of dimethylformamide and
15 parts of triethylamine were added. The reaction mixture
was cooled to -10C, and 15 parts of thionyl chloride was
dripped in while stirring. The mixture was then stirred
overnight at room temperature. A solution of 12 parts of
triethylamine and 12 parts of aniline in 20 parts of methylene
chloride was dripped in at +10C with cooling. The mixture
was then refluxed for 1 hour. After the mixture had cooled,
the precipitate was filtered off and washed with methylene
chloride, and the organic phase was concentrated. The oil
which remained was filtered through silica gel using methylene
chloride as eluant, and 18 parts of a uniform oil was obtained
which crystallized after standing overnight in ether.
The yield was 15 parts of 2-(4'-chlorophenoxy)-
2-(1',2',4'-triazol-1'-yl)-acetic acid anilide of melting
point 134 to 136C.
EXAMPLE 2
23 parts of 2-(4'-phenylphenoxy)-2-(1',2',4'-triazol-
l'-yl)-acetic acid was suspended in 150 parts of tetrahydrofuran,
13 parts of N,N' carbonyldiimidazole was added in portions
to this suspension. After the mixture had been stirred for
1 hour at room temperature, a solution of 9 parts of 4-fluoro-
aniline in 20 parts of tetrahydrofuran was dripped in. The
mixture was stirred for 12 hours and then stirred into 1,000
parts of ice water, and the precipitate was filtered and dried.
There was obtained 26 parts of 2-(4'-phenylphenoxy)-
2-(1',2',4'-triazol-1'-yl)-acetic acid-p-fluoroanilide of
melting point 92 to 96C.
1~3Z5~30
Table
No. Rl R2 R R4 X y Fp/nD20
3 4-Cl-C H - H H H O OC (CH3) 2C--CH 91--94
4 2,4-DiBr-C6H3- H H H O OC (CH3) 2C--CH
2-Br-4-Cl-C H3- H H H O OC (CH3) 2C-CH
6 2,4-DiCl-C6ll3- H H H O OC (CH3) 2C~CH 60-63
7 2,4-DiCl-C6H3- H H H O NHC(CH3)2C--CH 112-115
8 2,4-DiCH3C6H3-- H H H O NHC (CH3) 2C--CH
4-Cl-C6H4- H H H O NHC (CH3) 2C-CH 74-82
3-F-C6H4- H H H O NHC (CH3) 2CH--CH2
11 2,4-DiCl-C6H3- H H H O NHC6H5 92--95
12 2,4-DiCH3-C6H3 H H H O NHC6H5 114-116
13 2,4-DiCl-C6H3- H H H O NH-2-F-C6H4 99-101
14 4-Br-C6H4- H H H O NH-2-F-C6H4
4-Cl-C6H4 H H H- O NH-3-F-C6H4 102-105
16 2,4-DiCl-C6H3-- H H H O NH--3-F-C6H4 80-84
17 3-CF3-C6H4- H H H O NH--3-F-C6H4
18 4-Cl-C6H4- H H H O NH-4-C6H4 138-142
20- 19 2,4,5-TriCl-C6H2-H H H o NH-4-F-C6H4 136-140
2,9-DiCl-C6H3- 1l ll H o N~l-4--F-C6H4139-142
21 4-Cl-C6H4-- H H H O NH-4-Cl-C6H4 146-149
22 2-Br-4Cl-C6H3- H H H O NH-4-Cl-C6H4
23 3-F-C6H4- H H H O NH-4-Cl-C6H4
24 2,4-DiCl-C6H3- H H H O NH-2,4-DiF-C6H3122-124
3,4-DiCl--C6H3-- H H H O NH--3,4-DiF-C6H3
26 2,4 DiCH3 C6H3 H H o NH-3Cl-4F-C6H3
27 2,4--DiCl--C6H3-- H H H O NH-3,5-DiCl-C6EI3 170-173
28 3 CHF2 CF2 C6H4 H H H O NH-3,5--DiCl-C6H3
4-CH3-C6H4 H H H O NH-2-CH3-C6H4
2,4-DiCl-C6H3- H H H O ~I 2 i C3H7 C6H4 90 9
31 4-Cl-C6H4- H H H O NH-3-tert-C4Hg-
C6H4 153-158
-- 10 --
1~32580 -
Table
No. Rl R2 R3 R4 X y Fp/nD
32 2,4-DiC1~6H3- H H H O NH-3-tert 4 9 154-155
33 4-Cl-C6H4- H H H O NH-3-CF3~6H4 121-124
34 4-tert-C4H9-C6H4 H H H O NH-3-CF3-C6H4
2,4-DiC1-C6H3~ H ll H O NH-3CF3-C6H4 115-122
36 4-C1-C6H4- H H H O N(CH3)C6H5 oil
37 3-F-C6H4- H H H S N(CH3)C6H5
10 38 4-Cl-C6H4- H H H O N (CH3) -4-Cl-C6H4 125--127
39 2,4-DiCl-C3H3- H H H O N~l-CH2-C6H5 72-75
4-C1-C6H4- H H H O N(CH3)CH2C6H5 1,5652
41 4-Cl-C6H4- H H H O NH-~ 144-146
/CH3
42 2,4-DiC1-C6H3-- H H H O N 106-108
.. 1/(0
43 4-Cl-C6H4-- H H H O NE~ 152-156
20 44 4-C1-C6H4- H H H O N~ 1, 526
CH3 3
4-Cl-C6H4- H H H O N ~ F 1,530
CH3 Cl
46 4-F-C6H4-- H H H O N~ 102--110
47 2,4-DiCl-C6H3- H H H O N(~H3)C6H5 145-148
48 2,4-DiC1-C6H3- H H H O N-CH2 CH~12 76-77
49 3,5-DiCH3-C6H3- H H H o N(CH3)C6H5 101-103
4-tert-C4HgH4- H H H O NH-4F-C6H4 123-125
:113Z5~30
Table
No. Rl R2 R3 R X Y Fp/~
, _ .
51 2,4-DiCl-C6H3- H H H O N-2,4-DiCl-C6H3 109-111
CH3
52 4-Cl-C6H4- H H H O N(CH2CH2CN) 2 1,529
53 ~ H H H O NH-C6H5 120-123
54 4-Cl-C H4- H H H O N-C6H5 74-76
CH2-C6H5
4-Cl-C6H4- H H H O N(CH2-CH=CH2) 2 1,5280
56 ~ H H H O NH-C6H5 110-113
57 2,4,5-TriCl-C6H2- H H H O NHC (CH3) 2C=CH 176-185
58 4-F-C6H4- H H H - O NH-4F-C6H4 127-135
59 ~ H H H O ~ 105-111
~) .
2,4,5-TriCl-C6H2 H H H O NHCH~ - ~ 168-172
20 61 ~ H H H O NH-C6H5 158-163
62 ~ H H H O ( 3)C6H5 69-74
63 2,4-DiCl-C6H3 H H H NH-CH-C6H5 102-103
CH3
64 2,4-DiCl-C6H3- H H H O NH-CH2 - 2Cl - C6H~ 102-105
3-tert-C4Hg-C6H3- H H H O NHC6H5 103-106
66 ~ H H H O NH-4Cl-C6H4 120-125
67 ~ H H H O NHCH2C6H5 71-76
- 12 -
113ZSt30
Table
No. Rl R2 R3 R4 X Y Ep/~0
_
68 ~_ H H H O N (CH2-CH=CH2) 2 49~54
69 (~_ H H H O NH--3CF3~6H4120-12S
-- 13 --
, "
,,
1~ 3;~0
The manufacture of the metal complexes is illustrated
by the following non limitative example.
EXAMPLE 70
17 parts of 2-(4'-phenylphenoxy)-2-(1',2',4'-
triazol-l'-yl)-acetic acid-4-fluoroanilide was dissolved in
200 parts of ethanol at 35C; a solution of14 parts of
copper (II) chloride in 100 parts of ethanol was then added.
The mixture was stirred for 2 hours and cooled to 15C, and
the precipitate filtered.
There was obtained 13 parts of bis-~2-(~'-phenyl-
phenoxy)-2-(1',2',4'-triazol-1'-yl)-acetic acid-4-fluoro-
anilid~ -copper (II) chloride of melting point 176 to 180C.
The other compounds can be converted into their
metal complexes in analogous manner.
The compounds according to the invention and their
salts and metal complexes have an excellent action on a broad
spectrum of fungi, expecially plant-pathogenic fungi, particul-
arly from the Ascomycetes and Basidiomycetes classes. Some
of them have a systemic action and may be used as foliar and
soil fungicides.
The fungicides according-to the invention are of
particular interest for combatting numerous fungi in various
crop plants or their seed.
By " crop plants" , we mean in the connection in
particular wheat, rye, barley, oats, rice, Indian corn,
cotton soybeans, coffee, sugarcane, fruit and ornamentals in
horticulture, and vegetables such as cucumbers, beans and
Cucurbitaceae.
The new compounds are especially su~itable for
combatting the following diseases: Erysiphe graminis in
cereals, Erysiphe cichoriacearum in Cucurbitaceae,
Posdosphaera leucotricha in apples, Uncinula necator in grapes,
ErYsiphe polygoni in beans, Sphaerotheca pannosa in roses,
Puccinia species in cereals, Rhizoctonia solani in cotton,
- 14 -
~3Z58()
Helminthosphorium species in cerials, Ustilago species in
cereals and sugarcane, Rhynchosporium secale in cereals, and
Venturia inaequalis (apple scab).
The compounds are applied by spraying or dusting
the plants with the activc inc3redients or treating their sced
with them. They may be applied before or after infection of
the plants or seed by the fungi.
The compounds of the invention can be converted
into the conventional formulations, e.g. solutions, emulsions,
suspensions, dusts, powders, pastes and granules. The form
of application depends entirely on the purpose for which the
agents are being used; it should, however, ensure a fine
and uniform distribution of the active ingredient. The formul-
ations are prepared in the conventional manner, for example
by diluting the active ingredient with solvent and/or carriers,
with or without the addition of emulsifiers and dispersants
and, where water is used as the diluent, with or without organic
auxiliary solvents. Suitable auxiliaries are, essentially,
solvents for example aromatics, e.g., xylene and benzene,
chloroaromatics, e.g. chlorobenzene, paraffins, e.g. petroleum
fractions, alcohols, e.g. methanol and butanol, amines, e.g.,
ethanolamine, dimethylformamide, and water; solid carriers,
for example natural rock powders, e.g. kaolin, alumina, talc
and chalk, and synthetic rock powders, e.g. highly disperse
silica and silicates; emulsifiers, for example non~ionic and
anionic emulsifiers, e.g. polyoxyethylene fatty alcohol ethers,
alkylsulfonates and arylsulfonates, and dispersants, for example
lignin, sulfite waste liquors and methylcellulose.
The agents in general contain from 0.1 to 95%
by weight of active ingredient, preferably from 0.5 to 90~.
The application rates depend on the type of effect
desired, and are from 0.01 to 3, but preferably from 0.01 to
- 15 -
~3Z580
l, kg of active ingredient per hectare.
The agents, and the ready-to-use preparations
obtained therefrom, e.g., solutions, emulsions, suspensions,
powders, dust, pastes or granules, are applied in conventional
manner, e.g. by spraying, atomizing, dusting, broadcasting,
dressing seed, or watering.
Examples of such formulations are as follows.
I. 90 parts by weight of the compound of Example 6 is
mixed with 10 parts by weight of N-methyl-~-pyrrolidone. A
mixture is obtained which is suitable for application in the
form of very fine drops.-
II. 20 parts by weight of the compound of Example 32 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 with 1 mole of oleic acid-N-monoethanolamide,
5 parts by weight of the calcium salts 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 con-
taining 0.02~ by weight of the active ingredient.
III. 20 parts by weight of the compound of Example 17 is
dissolved in a mixture 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 with 1 mole
of isooctylphenol, and 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 of water and
finely distributing it therein, an aqueous dispersion is
obtained containing 0.02~ by weight of the active ingredient.
IV 20 parts by weight of compound of Example 56 is
dissolved in a mixture consisting of 25 parts by weight of
- 16 -
58~;)
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 l mole
of castor oil. By pouring the solution into lO0,000 parts by
weight of water and uniformly distributing it therein, an
aqueous dispersion is obtained containing 0.02% by weight of
the active ingredient.
V. 20 parts by weight of the compound of Example 58
is well mixed with 3 parts by weight of 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 distrib-
uting the mixture in 20,000 parts by weight of water, a spray
liquor is obtained containing 0.1~ by weight of the active
ingredient.
VI. 3 parts by weight of the compound of Example 30 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 the compound of Example 2
is intimately mixed with 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.
VIII. 40 parts by weight of the compound of Example 1
is intimately mixed with 10 parts of the sodium salt of a
phenolsulfonic acid-ureà-formaldehyde condensate, 2 parts of
silica gel and 48 parts of water to give a stable aqueous
dispersion. Dilution in lO0,000 parts by weight of water
gives an aqueous dispersion containing 0.04 wt% of active
113;2~8~
ingredient.
IX. 20 parts of the compound of Example 2 is intimately
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.
The above ready-to-use preparations may contain
other active ingredients together with those according to the
invention, e.g., herbicides, insecticides, growth regulators
and other fungicides or may be mixed with fertilizers and
applied together with these. When the active ingredients are
mixed with other fungicides, the fungicidal spectrum of action
is in many cases broadened.
The list of fungicides given below, with which the
compounds according to the invention can be combined, is
intended to illustrate the possible combinations, but the
invention is in no way limited to these.
Examples of fungicides which may be combined with
the compounds according to the invention are as follows.
~ ithiocarbamates and derivatives thereof, such as
ferric dimethyldithiocarbamate
zinc dimethyldithiocarbamate
manganese ethylenebisdithiocarbamate
zinc ethylenebisthiocarbamate
tetramethylthiuram disulfide
manganese-zinc ethylenediamine-bisdithiocarbamate
zinc-(N,N'-propylene-bisdithiocarbamate)
ammonia complex of zinc-(N,N'-ethylene)-bisdithiocarbamate
and
N,N'-polyethylene-bis-(thiocarbamoyl)-disulfide
ammonia complex of zinc-(N,N'-propylene-bisdithiocarbamate)
- 18 -
ll~Z580
and
N,N'-polypropylene-bis-(thiocarbamoyl)-disulfide
nitro derivatives, such as
dinitro-(l-methylheptyl J -phenylcrotonate
2-sec-butyl-4,6-dinitrophenyl-3,5-dimethylacrylate
2-sec-butyl-4,6-dinitrophenylisopropylcarbonate
heterocyclic structures, such as
N-trichloromethylthiotetrahydrophthalimide
N-trichloromethylthiophthalimide
2-heptadecyl-2-imidazoline acetate
2,4-dichloro-6-(o-chloroanilino)-s-triazine
0,0-diethylphthalimidophosphorothionate
5-amino-1-rbis-(dimethylamino)-phosphinyl~-3-phenyl-1,2,4-
triazole
5-ethoxy-3-trichloromethyl-1,2,4-thiadiazole
2,3-dicyano-1,4-dithiaanthraquinone
2-thio-1,3-dithio-(4,5b)-quinoxaline
methyl l-(butylcarbamoyl)-2-benzimidazole carbamate
~2-methoxycarbonylaminobenzimidazole
2-thiocyanomethylthiobenzothiazole
4-(2-chlorophenyl~ydrazono)-3-methyl-5-isooxazolone
pyridine-2-thiol-1-oxide
8-hydroxyquinoline and its copper salt
2,3-dihydro-5-carboxanilido-6-methyl-1,4,-oxathin-4,4-dioxide
2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin
2-~furyl-(2 U-benzimidazole
piperazine-1,4-diyl-biS~1-(2,2,2-trichloroethyl)-formamide~
2-Lthiazolyl-(4)~-benzimidazole
5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine
bis-(p-chlorophenyl)-3-pyridinemethanol
1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene
1,2-bis-(3-methoxycarbonyl)-2-thioureido)-benzene
- lg -
1~32580
and various fungicides, such as
dodecylguanidine acetate
3-l2-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl~7-glutarimide
hexachlorobenzene
N-dichlorofluoromethylthio-N,N'-dimet]lyl-N-phenylsulEurlc acld
diamide
2,5-dimethyl-furan-3-carboxylic acid anilide
2,5-dimethyl-furan-3-carboxylic acid cyclohexylamide
2-methyl-benzoic acid anilide
2-iodo-benzoic acid anilide
1-(3,4-dichloroanilino)-1-formy~amino-2,2,2-trichloroethane
2,6-dimethyl-N-tridecyl-morpholine and its salts
2,6-dimethyl-N-cyclododecyl-morpholine and its salts
DL-methyl-N-(2,6-dimethylphenyl)-N-furoyl-(2)-alaninate
DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl-alanine methyl
ester
diisopropyl 5-nitroisophthalate
1-(1',2',4'-triazolyl 1')-~1-(4'-chlorophenoxy)~-3,3-dimethyl-
butan-2-one
1-(1',2',4'-triazolyl-1')-~1-(4'-chlorophenoxy)_7-3,3-dimethyl-
butane-2-ol
N-(2,6-dimethylphenyl)-N-chloroacetyl-D,L-2-aminobutyrolactone
and
N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolylurea.
The following examples demonstrate the biological
action of the new compounds. The agent used for comparison
purposes was t-butyl 2-phenyl-2-(1',2',4'-triazol-1'-yl)-
acetate (N) disclosed in German Laid-Open Application
DE-OS 2,638,470.
EXAMPLE A
Leaves of pot-grown wheat seedlings of the " Caribo"
variety are sprayed with aqueous emulsions consisting of 80
-20 -
~3~,58~
(by weight) of active ingredient and 20% of emulsifier, and
dusted, 2 days after the sprayed-on layer has dried, with
spores of wheat mildew (Erysiphe graminis var. tritici). The
plants are then placed in a greenhouse at 18 to 24C. The
extent of mildew spread is determined after 10 days.
- 21 -
113;~580
Compound from Leaf attack after spraying with liquor
Example No. containing active ingredient in amounts of
0.025~ O.Oi2% 0.006
0 0 0
2 0 0 0
3 0 2 3
11 0 0 2
12 1 1 2
13 0 0 0
14 0 1 2
0 0 2-3
33 0 0
0 2 2-3
38 0 0 2
39 0 0 0
41 0 0 2
42 0 1 2
43 0 0 0
44 0 0 3
0 0 0
46 0 0 0
48 0 0 0
52
53 0 0 0
54 0 0 0
0 0 0
56 0 0 2
58 0 0 0
59 0 0 0
0
61 ~ 0 0
62 0 0 0
63 0 0 0
: 1~3'~580
Compound from Leaf attack after spraying with liquor
Example No. containing active ingredient in amounts of
0.025 0.012% 0.006%
64 0 0 0
0 2 2
66 0 ~ 2
67 0 0 0
68 0 0 0
69 0 0
0 0 0
N 2 3 4
Control (untreated) 5
0 = no fungus growth, graduated down to 5 = leaf surface
totally covered with fungus
EXAMPLE B
Leaves of wheat plants grown in pots are artificially
infected with spores of Puccinia recondita, and placed for
48 hours in a steam-saturated chamber at 20 to 25C. The
plants are then sprayed with aqueous liquor containing, as a
solution or emulsion in the water, a mixture of 80% of the
compound to be investigated and 20% of sodium ligninsulfonate.
The plants are then set up in the greenhouse at from 20 to .
22C and a relative humidity of 75 to 80%. The e~tent of
fungus spread is assessed after 10 days.
- 23 -
S80
Compound from Leaf attack after spraying with liquor con-
Example No. taining active ingr~dient in amounts of
0.025% 0.01~% 0.006%
2 0 0 0
59 0 0
61 0 0 0
62 0 0
66 0 0 0
68 0 0
0 0
Control (untreated) 5
0 = no fungus growth, graduated down to 5 = leaf surface totally
covered with fungus~
- 24 -
