Note: Descriptions are shown in the official language in which they were submitted.
` ~13~465
The present invention relates to azolyl ketals of the formula I
=N
Rl - C - Cll N / ¦ (I),
o o b x=.
\ A 2
including salts thereof which are tolerant to plants, with inorganic or
organic acid selected from the group consisting of hydrochloric acid, hydro-
bromic acid, hydriodic acid, sulfuric acid, phosphoric acid, nitric acid,
acetic acid, trifluoroacetic acid, trichloroacetic acid, oxalic acid, benzene-
sulfonic acid and methanesulfonic acid, and metal complexes with the halides,
nitrates, sulfates, phosphates or tartrates of copper, manganese, iron or zinc,
in which formula
Rl is tertiary butyl, or phenyl which is unsubstituted or mono- or
disubstituted by halogen,
R2 is phenyl or diphenyl which in each case is unsubstituted or
substituted by 1 to 3 halogen atoms, Cl-C2-alkyl, methoxy, cyano,
nitro and/or phenoxy, and
: A is -CH - CH- or -CH C - CH2- wherein
R3 R4 R5 R6
R3, R4, R5 and R6 independently of one another are each hydrogen,
Cl~.C6-alkylj Cl-C6-alkoxymethyl or phenoxymethyl, or
R3 and R4 together are tetramethylene, and
X is CH or N.
By alkyl or by alkyl part of another substituent are meant, depend-
ing on the given number of carbon atoms the following groups: methyl, ethyl,
propyl, butyl, pentyl or hexyl, and also isomers thereof (such as iso-propyl,
iso-butyl, sec-butyl, tert-butyl, iso-pentyl, and so forth).
--1--
113~4~S
,
Halogen is fluorine, chlorine, bromine or iodine.
The suitable salt-forming acids are: hydrochloric acid, hydro-
bromic acid, hydriodic acid, sulfuric acid, phosphoric acid, nitric acidJ
acetic acid, trifluoroacetic acid, trichloroacetic acid, oxalic acid, benzene-
I sulfonic acid and methanesulfonic acid.
Metal complexes of the formula I consist of the basic organic
molecule and an inorganic or organic metal salt, selected from the halides,
nitrates, sulfates, phosphates and tartrates of copper, manganese, iron and
zinc. The metal cations can be present here in the various valencies in which
they occur.
Compounds of the formula I are very valuable active substances
against phytopathogenic microorganisms.
i A preferred subgroup of effective fungicides is formed by those
compounds of the formula I wherein Rl is tertiary butyl, or phenyl which is
~' unsubstituted or mono- or disubstituted by fluorine or chlorine, R2 is phenyl
or diphenyl which in each case is unsubstituted or substituted by 1 or 2
halogen atoms, and A is -CH - CH- or -CH2 /C _ CH2-, wherein R3~ R4,
- R3 R4 R5 R6
R5;and R6 independently of one another are each hydrogen, Cl-C3-alkyl, methoxy-
' 20 methyl
. ~ .
~;31,
113~34~5
or phenoxymethyl, or R3 and R4 together are tetramethylene,
and X is CH or N.
Another subgroup of effective fungicides is formed by
those compounds of the formula I wherein Rl is tertiary
butyl or 2,4-dichlorophenyl, R2 is a phenyl group which
is unsubstituted or substituted by methyl, chlorine,
methoxy, cyano or phenoxy, and R3 and R4 together form
a tetramethylene bridge.
A further subgroup of effective fungicides is formed
by those compounds of the formula I wherein Rl is tertiary
butyl or 2,4-dichlorophenyl, R2 is a phenyl group which is
unsubstituted or substituted by methyl, chlorine, methoxy,
cyano or phenoxy, and A is -CH(R3)-CH(R4)-, where R3 is
hydrogen, and R4 is Cl-C6-alkoxymethyl or phenoxymethyl,
the Cl-C3-alkoxymethyl groups being preferred among the
possible alkoxymethyl side chains.
A preferred subgroup of effective fungicides consists
of those compounds of the formula I wherein Rl is tertiary
butyl or 2,4-dichlorophenyl, R2 is a phenyl group which
is mono- or disubstituted by chlorine, A forms an ethylene
bridge which is unsubstituted or substituted by Cl-C3-
alkyl or methoxymethyl, and X is CH or N.
Particularly preferred however are those fungicides
which correspond to the formula I wherein Rl is tertiary
butyl, R2 is a phenyl group which is mono- or disubstituted
by chlorine, A is an ethylene bridge, and X is CH or N.
The following individual compounds are particularly
preferred:
2-tert-butyl-2-[1-(4-chlorophenoxy)-1-(1,2,4-triazol-1-yl]-
methyl-1,3-dioxolane,
2-tert-butyl-2-[1-(4-chlorophenoxy)-1-(imidazol-1-yl)]-
methyl-1,3-dioxolane,
~138465
2-tert-butyl-2-[1-(phenoxy)-1-(1,2,4-triazol-1-yl)]-methyl-1,3-dioxolane,
2-tert-butyl-2-rl-(4-fluorophenoxy)-1-~1,2,4-triazol-1-yl)]-methyl-1,3-dioxolane,
2-(2,4-dichlorophenyl)-2-[1-(4-chlorophenoxy)-1-~1,2,4-triazol-1-yl)]-methyl-1,
3-dioxolane,
2-tert-butyl-2-[1-~2,4-dichlorophenoxy)-1-(1,2,4-triazol-1-yl)]-methyl-1,3-
dioxolane.
In accordance with further subject matter of the present invention,
the compounds of the formula I are produced by reacting a compound of the
formula II
Rl ~ C\ - CH -~~ R2 (II)
\ /0 Hal
with a compound o the formula III
MeN / l (111~
wherein Rl, R2, X and A have the meanings given under the formula I, "Hal"
is halogen, preferably chlorine or bromine, and Me is hydrogen or an alkali
metal cation or alkaline-earth metal cation (for example potassium or sodium).
The process is performed in the presence of an aprotic polar solvent
which is inert to the reactants. Examples of solvents of this type are acetoni-
trile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethyl-
phosphoric acid triamide or sulfolane.
In the cases where Me in the formula (III) is hydrogen, the process
is performed in the presence of a base. Examples of suitable bases are in-
organic bases such as the oxides, hydroxides, hydrides, carbonates and hydrogen
-! ~
11384~S
carbonates of alkali metals and alkaline-earth metals,
as well as for example tert. amines, such as triethyl-
amine, triethylenediamine, pyridine, 4-dimethylamino-
pyridine, 4-pyrrolidylpyridine and diazabicyclooctane.
The process is performed between 0 and 150C and
under normal pressure.
The starting ketals of the formula II are produced
by reacting
a) a compound of the formula IV
Rl- c - CH20 - R2 (IV)
with a diol of the formula V
HO--A--OH (V)
in the presence of an acid; and
b) halogenating the resulting ketal of the formula VI
o, ,b 2 2 ~VI).
A
The solvents used are solvents inert to the reactants:
for example, for reaction a) hydrocarbons such as benzene,
toluene and halogenated hydrocarbons (carbon tetra-
chloride, chloroform, methylene chloride, dichloroethane,
and so forth); or for reaction b) halogenated hydrocarbons
(carbon tetrachloride, chloroform, methylene chloride, and
so forth), diethyl ether, tetrahydrofuran, dioxane, and
the like.
Suitable acids in the case of process a) are for
example mineral acids such as HBr, HCl and H2S04, and also
p-toluenesulfonic acid and boron trifluoride etherate.
Halogenating agents suitable for process b) are for
113B465
-- 6 --
example: chlorine, sulfuryl chloride, bromine or N-bromo-
- succinimide; and with the use of N-bromosuccinimide or
chlorine, catalysts can be used (for example light,
peroxide such as dibenzoyl peroxide, or a,a'-azoiso-
butyronitrile).
The reaction temperatures in the case of the partial
step a3 are 40 to 150C, the reaction being advantageously
performed using a water separator. In the process b),
the reaction temperaturesare 0 to 100C, preferably
35 to 70C. The process steps a) and b) comprising
respectively ketalising and halogenating of the pinacoline
ethers IV (Rl = tert-butyl) to intermediates of the
formulae VI and II constitute an independent further
aspect of the present invention. This aspect is also an
independent method for producing pinacoline ether ketals
of the formula VI and halogenated ketals of the formula II.
The ketones on which the ketals of the formula I
are based have in individual cases become known by virtue
of German Offenlegungsschriften Nos. 2,325,156 and
2,705,676; German AuslegeSchrift No. 2,201,063; and
German Offenlegungsschrift No. 2,705, 678. They cannot
however be used as starting materials for the process
steps described herein.
The following Examples serve to further illustrate
the invention without limiting the scope thereof. The
temperature values are given in degrees Centigrade, and
pressure values in millibars. Percentages and parts
relate to weight.
. ' : '
1138~5
-- 7 --
Production Examples
~ Example 1
i Production of 2-tert-butyl-2-[1-(4-chlorophenoxy)-1-
(1,2,4-triazol-1-yl)]-methyl-1,3-dioxolane of the formula
.
CH3~ - ca - o--\O\--cl (compound No. 18)
3 ~
a) Production of 2-tert-butyl-2-[1-(4-chlorophenoxy)]-
methyl-1,3-dioxolane of the formula
CH--~3 \C/-- CH -O--/O\--C
~- 3
~`~ 40 g of 4-chlorophenoxypinacoline and 17 g of ethylene
glycol, with the addition of 0.2 g of p-toluenesulfonic
acid in 300 ml of toluene, were refluxedfor 30 hours using a
- water separator. The cooled toluene solution was washed
successively with diluted bicarbonate solution and with
water; it was then dried with sodium sulfate, filtered and
concentrated in vacuo. The crystals obtained in this way
were recrystallised from petroleum ether, and yielded
35 g of the intermediate, m.p. 68-70.
',` b) Production of 2-tert-butyl-2-11-(4-chlorophenoxy)-1-
bromine]-methyl-1,3-dioxolane of the formula
CH--~ --\C/--CH----/\O\--C
H3 r
24 g of 4-chlorophenoxypinacoline-ethylene ketal of
step a) was dissolved in 150 ml of tetrachloromethane, and
there was slowly added dropwise at 40-50C about 16 g of
1138465
bromine. The bromine was consumed after 15 hours' stirring
at this temperature. After cool:ing, the tetrachloro-
methane solution was washed with diluted bicarbonate
solution, dried, and concentrated by evaporation. From
petroleum ether, the residue yielded 18 g of product,
m.p. 118-120.
c) Final product
3 g of 1,2,4-triazole and 2 g of 55% sodium hydride
suspension in paraffin oil were placed together in
absolute dimethylformamide. After completion of the
evolution of hydrogen, stirring was maintained for 1 hour
at 80-100. There was then added dropwise 11 g of 2-tert-
butyl-2-[1-(4-chlorophenoxy)-1-bromine]-methyl-1,3-dioxolane
in dimethylformamide, and the reaction mixture was stirred
for 18 hours at 100-120. The solvent was removed in vacuo,
and the oily residue was taken up in ether, washed with
water, dried, filtered, and concentrated by evaporation.
There was obtained from the ether solution, after concen-
tration, 8 g of a viscous oil, which was purified by
chromatography on a silica gel column. There were obtained
in this manner colourless crystals of the compound No. 18,
m.p. 103-105.
Example_2
Production of 2-tert-butyl-2-[1-(4-chlorophenoxy)-1-
(imidazol-l-yl)]-methyl-1,3-dioxolane of the formula
3 ~ C311 --,~O~- CI ~compound No. 1)
~ Y
Final product
3 g of imidazole and 2 g of 55% sodium hydride suspen-
sion in paraffin oil were placed together in absolute
1138~65
dimethylformamide. After completion of the evolution
of hydrogen, s.irring was maintained for 1 hour at
80-100. There was then added dropwise 11 g of 2-tert-
butyl-2-[1-(4-chlorophenoxy)-1-bromine]-methyl-1,3-
dioxolane in dimethylformamide, and the reaction mixture
was stirred for 18 hours at 100-120. The solvent was
removed in vacuo; and the oily residue was taken up in
ether, washed with water, dried, filtered, and concentrated
by evaporation. There was obtained from the ether
solution, after concentration by evaporation, 9 g of a
viscous oil, which yielded, after recrystallisation from
hexane, colourless crystals of the compound No. l;
m.p. 102-104.
Example 3
Production of 2-(2,4-dichlorophenyl)-2-[1-(4-chloro-
phenoxy)-l-(1,2,4-triazol-1-yl)]-methyl-1,3-dioxolane
of the formula
Cl--~ ~ o~ Cl (compound No. 35)
a) Production of 2-(2,4-dichlorophenyl)-2-~1-(4-chloro-
phenoxy)]-methyl-1,3-dioxolane of the formula
/Cl ~
Cl ~ \C/--CH2--O --~ ~--Cl
A mixture of 54 g of a-(p-chlorophenoxy)-2,4-dichloro-
acetophenone, 20 ml of ethylene glycol and 2 g of p-
toluenesulfonic acid in 400 ml of toluene was refluxed using
a water separator. After a reaction time in each case
of 10 hours, a further 10 ml of ethylene glycol was added.
113~4~5
- 10 -
After 50 hours, the reaction mix~ure was cooled to room
temperature; it was subsequently washed once with sodium
bicarbonate solution and twice with water; the toluene
phase was then separated, dried over sodium sulfate, and
concentrated by evaporation to thus yield 61 g of a light-
yellow viscous oil.
b) Production of 2-(2,4-dichlorophenyl)-2-[1-(4-chloro-
phenoxy)-l-brominel-methyl-1,3-dioxolane of the formula
/Cl ~
Cl~ - \C/- ~ - o~ --Cl
.~. r '-
100 g of 2-(2,4-dichlorophenyl)-2-[1-(4-chlorophenoxy)]-
methyl-1,3-dioxolane was dissolved in 400 ml of absolute
dioxane, and there was then added dropwise at 70, with
stirring, 46 g (15 ml) of bromine. After 5 hours, the
reaction mixture was cooled to room temperature, and was
then poured into 2 litres of ice-water, this containing
20 g of sodium bicarbonate. The oil which had precipitated
was extracted with dichloromethane, the organic phase was
washed with aqueous sodium bicarbonate solution, and
dried over sodium sulfate. The yield was 130 g of a brown
oil, which was taken up in 500 ml of hexane. There
precipitated from this solution 78 g of beige-coloured
crystals, m.p. 100-104. :
c) Final product
37 g of 1,2,4-triazole potassium was added to a
solution of 77 g of 2-(2,4-dichlorophenyl)-2-l1-(4-chloro-
phenoxy)-l-bromine]-methyl-1,3-dioxolane in 500 ml of
absolute dimethylformamide, and the reaction mixture was
stirred for 15 hours at 100. After removal of the dimethyl-
formamide in vacuo, the brown residue was extracted with
, ~
113E~465
water and hexane/dichloromethane (8:2 parts by volume).
The organic extracts were dried over sodium sulfate, and
concentrated by evaporation. The yield was 62 g of a
dark-brown oil, from which was obtained, after purification
using an aluminium oxide (activity 2-3) column, 30 g of
a yellowish crystal mass of the compound No. 35,
m.p. 104-107.
Example 4
Production of 2-tert-butyl-2-~1-(2,4-dichlorophenoxy)-1-
(1,2,4-triazol-1-yl)]-methyl-1,3-dioxolane of the
formula
3 ~ 0~ Cl (Compound No. 26)
a) Production of 2-tert-butyl-2-[1-(2,4-dichlorophenoxy)]-
methyl-1,3-dioxolane of the formula
CU3~ c/- cu~-o~ --c~
50 g of 2,4-dichlorophenoxypinacoline with 20 g of
ethylene glycol and 0.5 g of p-toluenesulfonic acid in
300 ml of toluene was refluxed for 24 hours using a water
separator. The solution cooled to room temperature was
washed with aqueous sodium bicarbonate solution and then
~; with water; it was subsequently dried with sodium sulfate,
and concentrated in vacuo to yield 55 g of colourless
crystals, m.p. 61-63.
. ...
113~6'~
- 12 -
b) Production of 2-tert-butyl-2~ (2,4-dichlorophenoxy)-
l-bromine]-methyl-1,3-dioxolane of the formula
CH3~ H--O~ Cl
.~.
200 g of 2,4-dichlorophenoxypinacoline ketal produced
according to a) was dissolved in 900 ml of absolute dioxanè,
and there was then added dropwise at 40-50, with stirring,
105 g of bromine, the bromine being consumed after 4
hours of stirring. Stirring was continued for 1 hour, and
the reaction solution was then poured into 5 litres of ice-
water containing 50 g of sodium bicarbonate. The crystals
which had precipitated were filtered off with suction,
dried, and recrystallised from hexane to yield 130 g of
colourless crystals, m.p. 99-102.
c) Final Product
38.5 g of 2-tert-butyl-2-[1-(2,4-dichlorophenoxy)-1-
bromine]-methyl-1,3-dioxolane was added to a solution of -
15 g of 1,2,4-triazole potassium in 250 ml of dimethyl-
sulfoxide, and stirring was maintained for 15 hours at ~ `
100C. The reaction solution was then cooled to room tem-
perature, and poured into water. The brown oil obtained
was extracted with diethyl ether, dried over sodium sulfate,
and purified with a silica gel column to yield 17 g of a
viscous oil, which was able to be crystallised by the
addition of petroleum ether. The resulting crystals of the
compound No. 26 were recrystallised from hexane/diethyl
ether, and had a m.p. of 106-108.
The following compounds of the formula I can be
produced in an analogous manner:
A ~ (I)
... .
1138465
- 13 -
'' lc~ C~
Table I (X=CH; A~ - H-- H-)
. _ .___ . ~
Comp Rl R2 R3 R4 Physical
! No _ constants
1 t-butyl -C6H -Cl (4) H H m.p.102-104
2 t-butyl -C6H -C1(4) H H-V2 CuS04
3 t-butyl -C6H4-Cl(4) CH3 CH3 visc. oil
4 t-butyl -c H -Cl(4) H C3H7 (n)
5 t-butyl -C6H4-Cl(4) H ,2 3 .
6 t-butyl -C6H4-Cl(4) 2 H 2 ~}2
7 t-buty 1 -C6H3-C12(2,4) H H
8 t-butyl -C6H3-C12(2,4) H C2H5
9 t-butyl -C6H3-C12(2,4) H -CHzOcH3
10 t-butyl 6 5 H H visc. oil
11 t-butyl -diphenyl H C2Hs visc. oil
:: 12-C6H3-C12(2,4)-C6H -C1(4) H 3 7( )
13 6 4 ( )-C H -C1(4) H H resin
14 -C6H5 -C6H3-C12(2,4) H H
Table II (X-CH; A- -CH2 /C~-- CH2-)
R `R
Comp~ Rl R2 R5 R6 Physical
~: . No. . constants
: 15 t-butyl -C H -Cl(4) H H
16 -C6H3-C12(2,4) -C H4-C1(4) CH3 CH3 m.p.82-84C
17 -C6H4-F(4) 1 -C6H4-Cl(4) CH3 CH3 m.p.150-151
~13846S
Table III (X=N; A~ -~CH - ~H-)
3 4
Comp. Rl _ R3 R4 Physical
No. _ constants
18 t-butyl -C H -C1(4) H H m.p.103-105
19 t-butyl -c H -C1(4) H H 1/7 CuS04 m.p.195-198
t-butyl -C H -C1(4) H C2H5 m.p.110-115
21 t-butyl -C6H4-Cl(4) H 3 7( ) m.p. 90-92
22 t-butyl -C H -C1(4) CH 3 CH3 visc. oil
23 t-butyl -C6H -C1(4) H -CH -0-CH
24 t-butyl -C H -Cl(4) -CH -CH2-CH2-CH2- m.p.115-120
t-butyl -C H -C1(4) H -CH2-0-C6H5visc. oil
2 6 t-butyl -C6H3-C12(2,4) H H m.p. 106-108
27 t-butyl -C6H3-C12(2,4) H H~V2~n(N03)2
28 t-butyl -C6H3-C12(2,4) H -C2H5 visc. oil
29 t-butyl -C6H3-C12(2,4) H -CH2-0-CH3 resin
t-butyl -C6H5 H H visc. oil
31 t-butyl 6 4 ( ) H H visc. oil
32 t-butyl -diphenyl H C2H5visc. oil
33 6 5 -C6H3-C12(2,4) H H m.p.129-132
34 6 4 ( ) -C6H -C1(4) H H m.p.115-116
-C6H3-C12(2,4) -C H -C1(4) H H m.p.104-107
36 -C6H3-C12(2,4) -C6H3-C12(2,4) H H m.p. 94-97
37 -C6H3-C12(2,4) -C6H4-Cl(4) H -CH2-0-C~3
38 -C6H3-C12(2,4) -C H4-Cl(4) H C3H7(n)
.~ _
`~ ~
113t~465
- 15 -
Table IV (X-:~; A~ -CH2 ~C~ CH2
Comp. Rl R2 - R6 Physical
No. constants
_ _
39 t-butyl -C H -Cl(4) CH; C~j HCl visc. oil
t-butyl -C H -Cl(4) H H
41 -C6H3-C12t2,4) -C H -C1(4) C~3 CH3 m.p. 128-131
42 6 4 ( ) -C H -Cl (4) CH3 CH3 m.p. 134-138
The compounds of the formula I can be used on their
own or together with suitable carriers and/or other
additives. Suitable carriers and additives can be solid
or liquid and they correspond to the substances common in
formulation practice, such as natural or regenerated
mineral substances, solvents, dispersing agents, wetting
agents, adhesives, thickeners, binders or fertilisers.
Active substances of the formula I may also be used in
admixture with for example pesticidal preparations or
preparations improving plant growth.
The content of active substance in composition capable
of being sold commercially is between 0.0001 and 90%.
The compounds of the formula I can be applied in the
following forms:
Solid preparations
Dusts and scatterin~ a~ents contain in general up to
10% of active substance. A 5% dust can consist for
example of 5 parts of the active substance and 95 parts
of an additive such as talcum, or of 2 parts of the active
11384~S
- 16 -
substance, 1 part of highly dispersed silicic acid and
97 parts of talcum. In addition to these, other mixtures
with carriers and additives of this type and of other
types customary in formulation practice are conceivable.
These dusts are produced by mixing and grinding the active
substances with the carriers and additives, and they can
be dusted on in this form.
Granulates, such as coated granules, impregnated
granules and homogeneous granules, and also pellets,
usually contain 1 to 80% of active substance. Thus, a
5% granulate can for example be composed of 5 parts of the
active substance, 0.25 parts of epichlorohydrin, 0.25 part
of cetyl polyglycol ether, 3.50 parts of polyethylene
glycol and 91 parts of kaolin (preferred particle size
0.3 - 0.8 mm). The granulates can be produced as follows:
The active substance is mixed with epichlorohydrin, and the
mixture is dissolved in 6 parts of acetone; the polyethylene
glycol and cetyl polyglycol ether are then added. The
solution thus obtained is sprayed onto kaolin, and the
acetone is subsequently evaporated off in vacuo. A
microgranulate of this type is advantageously used for
combating soil fungi.
Liquid preparations
There is generally made a distinction between active-
substance concentrates which are dispersible or soluble
in water and aerosols. Water-dispersible concentrates of
active substance include for example wettable powders and
pastes, which usually contain in the commercial packing
25 - 90% of active substance, and in ready-for-use
solutions 0.01 to 15% of active substance. Emulsion
concentrates contain 10 to 50% of active substance, and
solution co centrates contain in the ready-for-use solution
0.0001 to 20% of active s~lbstance. A 70% wettable powder can
113846~
thus consist for example of 70 parts of active substance,
S parts of sodium dibutylnaphthyl sulfonate, 3 parts
of naphthalenesulfonic acid/phenolsulfonic acid/formal-
dehyde condensate (in the mixture ratio of 3;2:1), 10
parts of kaolin and 12 parts of Champagne chalk. A 40%
wettable powder can consist for example of the following
substances: 40 parts of active substance, 5 parts of
sodium lignin sulfonate, 1 part of sodium dibutyl-
naphthalene sulfonate and 54 parts of silicic acid. A 25%
wettable powder can be prepared in various ways. It can
thus be composed for example of: 25 parts of active
substance, 4.5 parts of calcium lignin sulfonate, 1.9 parts
of Champagne chalk/hydroxyethyl cellulose mixture 1:1,
1.5 parts of sodium dibutylnaphthyl sulfonate, 19.5
parts of silicic acid, 19.5 parts of Champagne chalk and
28.1 parts of kaolin. A 25% wettable powder may for example
also consist of 25 parts of active substance, 2.5 parts of
isooctylphenoxy-polyoxyethylene-ethanol, 1.7 parts of a
Champagne chalk/hydroxyethyl cellulose mixture 1:1, 8.3
parts of sodium silicate, 16.5 parts of kieselguhr and 46
parts of kaolin. A 10% wettable powder can be produced
for example from 10 parts of active substance, 3 parts of
a mixture of sodium salts of saturated fatty alcohol
sulfonates, 5 parts of a naphthalenesulfonic acid/formal-
dehyde condensate and 82 parts of kaolin. Other wettable
powders can be mixtures of 5 to 30% of active substance
together with 5 parts of an absorptive carrier material such
as silicic acid, 55 to 80 parts of a carrier such as kaolin
and of a dispersing agent mixture consisting of 5 parts of
sodium aryl sulfonate and of 5 parts of an alkylaryl-
polyglycol ether. A 25% emulsion concentrate can contain
for example the following emulsifiable substances: 25 parts
of active substance, 2.5 parts of epoxidised vegetable oil,
10 parts of an alkylaryl sulfonate/fatty alcohol polyglycol
,
;: ,
' -
1~3~465
- 18 -
ether mixture, 5 parts of dimethylformamide and 57.5
parts of xylene.
Emulsions of the required application concentration
can be produced from concentrates of the described types
by dilution with water, and these emulsions are par-
ticularly suitable for leaf application. In addition,
other wettable powders having different mixture ratios
or containing other carriers and additives common in
formulation practice can be produced. The active sub-
stances are intimately mixed in suitable mixers with the
additives mentioned, and the mixture is subsequently
ground in the appropriate mills and rollers. There are
obtained wettable powders which have excellent wetting
and suspension properties, which can be diluted with water
to give suspensions of the desired concentration, and
which can be used in particular for leaf application.
Compositions of this type also form subject matter of
the present invention.
It has been found that compounds having the structure
of the formula I surprisingly exhibit a very favourable
microbicidal spectrum for practical requirements for the
protection of cultivated plants. Cultivated plants within
the scope of the present invention are for example: cereals
(wheat, barley, rye, oats, rice, etc.); beet: (sugar beet
and fodder beet); pomaceous fruit, stone fruit and soft
fruit: (apples, pears, plums, peaches, almonds, cherries,
strawberries, rasberries and blackberries); legumes: (beans,
lentils, peas and soyabean); oil plants: (rape, mustard,
poppy,olives, sunflowers, coco, castor-oil plants, cocoa
and groundnuts); Cucurbitacea: (pumpkins, cucumbers and
melons); fibre plants: (cotton, flax, hemp and jute);
citrus fruits: (oranges, lemons, grapefruit and mandarins);
varieties of vegetables: (spinach, lettuce, asparagus,
varieties of cabbage, carrots, onions, tomatoes, potatoes
~ ,
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and paprika); or plants such as maize, tobacco, nuts,
coffee, tea, sugar beet, grapevines, hops, bananas
and natural rubber plants, and also ornamental plants.
Fungi occurring on plants or on parts of plants
(fruit, blossom, foliage, stalks, tubers or roots) of
the said crops and of related cultivated crops can be
inhibited or destroyed with the active substances of the
formula I, and also parts of plants subsequently growing
remain preserved from such fungi. The active substances
are effective against the phytopathogenic fungi belonging
to the following classes: Ascomycetes (for example
Erysiphaceae, Fusarium, Helminthosporium, Venturia and
Podosphaera); Basidiomycetes, such as in particular rust
fungi (for example Puccinia, Tilletia and Hemileia);
Fungi imperfecti (for example Moniliales, and so forth,
Cercospora as well as Botrytis and Verticillium), and the
Oomycetes belonging to the Phycomycetes class. Furthermore,
the compounds of the formula I have a systemic action.
They can also be used as dressing agents for treating
seed (fruits, tubers and grain), and plant cuttings to
protect them from fungus infections, and also against
phytopathogenic fungi occurring in the soil.
The invention hence relates also to the use of the
compounds of the formula I for controlling phytopathogenic
microorganisms, and/or for preventing infection on
plants.
Biolo~ical Examples
ExamPle 5: Action a~ainst Erysiphe ~raminis on barley
a) Residual protective action
Barley plants about 8 cm high were sprayed with a
spray liquor produced from wettable powder of the active
substance (0.02% of active substance). The treated plants
'
.
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were dusted after 3-4 hours with conidiospores of the
fungus. The infested barley plants were kept in a
greenhouse at about 22C, and the fungus infection was
assessed after 10 days.
b) SYstemic action
A spray liquor produced from wettable powder of the
active substance (o.oO6% of active substance, relative
to the volume of soil) was applied to the surface of the
soil of barley plants about 8 cm in height. Care was taken
to ensure that the spray liquor did not come into contact
with the parts of the plants above the soil. After 48
hours, the treated plants were dusted with conidiospores
of the fungus. The infested barley plants were kept in a
greenhouse at about 22C, and the fungus infection was
assessed after 10 days.
Example 6: Action a~ainst Puccinia ~raminis on wheat
a) Residual protective action
Six days after being sown, wheat plants were sprayed
with a spray liquor prepared from wettable powder of the
active substance (0.06% of active substance). After 24
hours, the treated plants were infested with a uredospore
suspension of the fungus. After an incubation time of
48 hours at about 20C with 95-100% relative humidity, the
infested plants were kept in a greenhouse at about 22C.
An assessment of the development of rust pustules was made
12 days after infestation.
b) Systemic action
A spray liquor produced from wettable powder of the
active substance (0.006% of active substance, relative to
the volume of soil) was applied to the soil of wheat plants
5 days after sowing. Af~er 48 hours, the treated plants
~ ~ .
1138465
- 21 -
were infested with a uredospore suspension of the fungus.
After an incubation time of 48 hours at about 20C w-th
95-100% relative humidity, the infested plants were kept
in a greenhouse at about 22C. An assessment of the
development of rust pustules was made 12 days after
infestation.
.,
Example 7: Action against Cercospora arachidicola on
~roundnut plants
/
Residual ~protective action
~,
Groundnut plants 10-15 cm in height were sprayed with
a spray liquor produced from wettable powder of the active
substance (0.02% of active substance); and 48 hours later
they were infested with a conidiospore suspension of the
fungus. The infested plants were incubated for 72 hours
at about 21C with high relative humidity, and were
subsequently kept in a greenhouse until the typical leaf
spots had appeared. The assessment of the fungicidal
action was made 12 days after infestation, and was based
on the number and size of the occurring spots.
:
ExamPle 8: Action against Venturia inaequalis on apple trees
Residual protective action
Young apple seedlings having about 5 developed leaves
were sprayed with a spray liquor produced from wettable
powder of the active substance (0.06% of active substance).
After 24 hours, the treated plants were infested with a
conidiospore suspension of the fungus. The plants were
incubated for 5 days with 90-100% relative humidity, and
were then kept for a further 10 days in a greenhouse at
20-24C. The extent of scab infection was assessed 15
days after infestation.
,
~138465
- 22 -
The compounds of the formula I according to theinvention exhibited in general a good fungicidal action
in the tests described in the foregoing. Thus, compared
with the infection on untreated but infested control
plants (= 100% infection), the infection on the treated
plants had been reduced to less than 20% by, among other
compounds of the formula I, those compounds of the invention
which are listed below:
against Puccinia ~raminis: Compounds Nos. 1, 3, 11, 13, 18,
19, 20, 21, 22, 24, 26, 28, 29, 30, 31, 32, 34, 35
and 39;
against Cercospora arachidicola: Compounds Nos. 1, 18, 20,
22, 26, 32 and 35;
against Erysiphe ~raminis: Compounds Nos. 1, 3, 11, 13, 17, 18,
19, 20, 21, 22, 24, 25, 26, 28, 29, 30, 31, 32, 33, 34,
35, 36 and 39; and
against Venturia inaequalis: Compounds Nos. 1, 3, 13, 18,
19, 20, 21, 22, 25, 26, 28, 29,30, 31, 32, 33, 34, 35,
and 39.
A reduction of infection to 5% and less was produced
in the above tests by the following compounds of the
formula I:
against Puccinia ~raminis: Compounds Nos. 1, 3, 13, 18, 19,
20, 22, 26, 28, 29, 30, 31, 35 and 39;
against Cercospora arachidicola: Compounds Nos. 1, 18, 20,
22, 26 and 35.
against ErYsiphe ~raminis: Compounds Nos. 1, 3, 13, 18, 19,
20, 21, 22, 25, 26, 28, 29, 30, 31, 32, 33, 34, 35
and 39; and
against Venturia inaequalis: Compounds Nos. 1, 18, 22, 26,
29, 30, 31, 35 and 39.
