Note: Descriptions are shown in the official language in which they were submitted.
21489 6188
~ he present invention relates to novel substituted azolyl-ethyl
ethers and acid addition salts thereo, to quaternary azolium salts and to
metal complexes. The invention relates also to the production oE these
substances, as well as to microblcidal compositions which contain as
active ingredient at least one of these compounds. The invention moreover
relates to the use of these active ingredients, or of the statecl composit-
ions, for combating harmful microorganisms.
There are embraced herein compounds of the general formula I
OR3
Rl~ - C~2 4
1.0 R2
wherein Rl is 2,4-dichlorophenyl, 2-chloro-4-fluorophenyl, 2-Eluoro-4-
chlorophenyl, 2-chloro-4-bromophenyl, 4-chlorophenyl or 4-fluorophenyl, R2
is C3-C6-cyclo-alkyl, or Cl-C4-alkyl, R3 is benzyl, chlorobenzyl, di-
chlorobenzyl, Cl-C4-alkyl or C3-C4-alkenyl and R4 is lH-1,2,4-triazolyl.
By 'alkyl' is meant, depending on the given number of carbon atoms,
Eor example the following groups: methyl, cthyl, propyl, butyl and isomers
thereoE, such as isopropyl, isobutyl and tert-butyl. Alkenyl is for example:
propellyl-(l), allyl, butenyl-(l), butenyl-(2) or butenyl-(3~. Cycloalkyl is,
depending Oll the number of carbon atoms, for example: cyclopropyl~ cyclobutyl,
cyclopentyl or cyclohexyl.
Thc compounds o-E the formula I at room temperature are stable oils,
resins or solids, which are distinguished by very valuable mlcrobicidal
properties. They can be used in agriculture or in related fields in a pre-
ventive and curative manner for comba-ting phytopathogenic microorganisms.
.~
5-13687/~
3~'7
--2--
The active substances oE ~he formula I according to the invention
are characterised by very good microbicidal activity, and by their great
ease of application.
Compounds of importance among those of formula I are those wherein
R3 is Cl-C4-alkyl, while Rl and R2 are as defined above.
Furthermore~ compounds of special importance are those wherein
R2 is methyl, iso-C3H7 or sec-C4~9, while Rl and R~ are as defined above.
Individual compounds preferred in particular are for example:
l-(lH-1,2,4-triazol-1-yl)-2-methoxy-2-~2,4-dichlorophenyl)-pentane,
1-(lH-1,2,4-triazol-1-yl)-2-allyloxy-2~2,4-dichlorophenyl)-pentane,
l-~lH-1,2,4-triazol-1-yl)-2-methoxy-2-(2-chloro-4-bromophenyl)-propane,
l-(lH-1,2,4-triazol-1-yl)-2-methoxy-2-(2,4-dichlorophenyl)-hex~ne,
l-(lH-1,2,4-triazol-1-yl)~-2-allyloxy-2-(2-chloro-4-fluorophenyl)-pentane,
l-(lH-1~2,4-triazol-1-yl)-2-methoxy-2-(2-chloro-4-Eluorophenyl)-pentane,
l-~lH-1,2,4-triazol-1-yl)-2-methoxy-2-(2,4-diclllorophenyl)-butane,
l-(lH-1,2,4-triazol-1-yl)-2-propoxy-2-(2,4-dichlorophenyl)-butane.
Azolyl-ethane derivatives of the formula I can be produced
according to the invention by reacting a compound of the formula II
Rl - I C112R4 (II)
R2
with a compolmd of the formula III
R~-W ~III)
wherein the substituen~s Rl, R2, R3 and R4 are as defined under the
formula I, A and W are each -OH, -OM or one of the customary removable
groups, M is an alkali metal atom or alkaline-earth metal atom, with
the proviso that the choice of the reactants II and III is always such
that either an MO or HO function reacts with a removable group or two
hydroxyl functions react with each other.
Prefera~ly, A or W as a removable group is halogen, -OS02R5~
-OCO-R5 or -0-C=NR6, wherein R5~ R6 and R7 independently of one another
NHR7
are each Cl-C3-alkyl or Cl-C3-haloal~yl, or phenyl which is unsubstituted
or substituted by halogen, methyl, nitro~ trifluoromethyl and/or methoxy.
In so far as alcohols, or alcoholates of the formula II are
concerned (A = OH or OM), compounds of the formula I will in practice be
produced by customary etherification with a compound of the formula III
wherein W is a halide, preferably a chloride or bromide. The reaction is
carried out in the temperature range of 0 to 150C~ either not in a
solvent or, pre:Eerably, in atropic solvents, such as aromatic and aliphatic
hydrocarbons, ethers and ethereal compounds ~diethyl ether, dioxane, tetra-
hydroEuran ~THF], al1d so forth~, acetonitrile, dimethylformamide [D~F~, and
'2() others familiar to the expert in the case of etheriEication reac~ions. To
be recommended also is the production in the phase-transfer process.
Alcohols of the formula Il (A = 0~1) are for the most part known
from the literature, or they can be produced by methods analogous to those
described therein. There are thus described as fungicides: l-phenyl-2-
(1~1-1,2,4--triazol-1-yl)-ethanol derivati-ves in the German Offenlegungsschrift
No. 3,042,302; and 2-(111-1,2,4-triazol-1-yl)-ethanol derivatives in the
EP Offenlegungsschrift ~oO 0,Ol5,756.
The compounds of the formula I according to the inventlon are
superior to the cited substances.
In all cases in which the substituents Rl and R2 in the compounds
of the formula are different, the compounds of the formula I contain, in the
position adjacent to ~he oxygen function, an asymmetric centre (*)
OR
j*3
Rl ~ 3 ~ - CH2- R~
R2
and can therefore be present in two enantiomeric forms. There is generally
formed in the production of these substances a mixture of both enantiomeric
forms; and this can then be separa-ted, by the customary methods of
enantiomer separation, for example by fractional crystallisation of a
diastereoisomeric salt mixture with an optically act;ve strong acid, or by
column-chromatography on an optically active carrier and with an optically
actlve eluting agent, into the optical antipodes. The two antipodes exhibit
a different microbicidal activity. ~xcept where specially emphasised, there
exists in all cases where reference is Inade to a compound of the formula I a
mixture oE both enantiomeric forms.
It has been shown that the active substances of the formula I, and
compositions containing them, exhibit~ for practical purposes, a very
favourable microbicidal spectrum, in particular against phytopathogenic fungi.
The compounds of the formula I thus have a very favourable curative, preven-
tive and systemic action Eor the protection of plants~ especially cultivated
.~ ,
plants, without aEfectin~ these in a disadvantageous manner.
The microorgani.sms occurring on plants or on parts of plants
(fruit, blossom, foliage, stalks, tubers or roots) of various 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 microorganisms. The acti.ve substances of the Eormula I are
effective against ~he phytopathogenic fungi belonging to the following
classes: Fungi imperfecti ~for example Botrytis, 1-3elminthosporium, Fusarium,
Septoria,Cercospora and Alternaria); Basidiomycetes (for example the species:
~1emileia, Rhi~octonia and Puccinia); in particular they are effective
against the Ascomycetes class (for example: Venturia, Podosphaera, Erysiphe,
Monilinia and ~ncinula). Furthermore, the compounds of the formula I have a
systemic action. They can be used also as dressing a.gents for the treatmen-t
of seed (fruits, tubers and grain), and of plant cuttings to protect them
from fungus infections, and also against phytopathogenic fungi occurring in
~he soil.
The i.nvention relates also to compositions which contain, as at
least one active ingredient, a compound of the formula I~ and also to the use
of these compositions, or of the active ingredients on their own, for com-
2() bating and/or preventing an infestation by microorganisms.
Within the scope of this invention, target crops with respect tothe range of indications disclosed herein include for example the following
species of cultivated plants: cereals: (wheat, barley, rye, oats, rice,
sorghum and related cereals); beet: (sugar beet and fodder beet); pomaceous
fruit, stone fruit and soft fruit: (apples, pears, plums, peaches, almonds,
cherries, strawberries, raspberries and blackberries); legumes: (beans,
lentils, peas and soya-bean); oil plants: (rape, mustard, poppy, olives,
--6--
sunflowers, coco, castor-oil plants, cocoa and groundnuts); Cucurbitacea:
(pumpkins, cucumbers and melons); fibre plants: (cotton, flax, hemp and
jute); ci.trus fruits: (oranges, lemons, gra.pefruit and mandarins); varieties
of vegetables: (spinach, lettuce, aspara.gus, varie~ies of cabbage, carrots,
onions, tomatoes, potatoes and paprika); laurel plants: (avocado, cinnamon
and camphor); or plants such as maize, tobacco, nuts, co:~fee, sugar beet,
tea, grapevines, hops, bananas and natural rubber plants. Plants wi.thin
the scope of the present invention are however also all types of o~her green
vegetation, whether it be in the form o-f ornamental plants (composites~,
areas of grass, embankments or general low cover crops.
Acti.ve substances of the formula I are customarily used in the
form of compositions, and can be applied, simultaneously or successively,
with further active substances to the area or plants to be treated. These
further active substances can be fertilisers, trace-element agents or
other preparations influencing plant growth. They can howeve-r also be
selective herbicides, insecticides, flmgicides, bactericides, nematicides or
molluscicides, or mixtures of several of these preparations, optionally
together with carriers commonly used in formulation practice, tensides or
other addi.t:ives fac:ilitating application.
2~ Suitable carriers and additives can be solid or liquid and they
correspond to tlle substances customarily employed ill :Formulation practice,
-.F.or example: natural or regenerated mineral substances, solvents, dispersing
agents, wetti:ng agents, adhesives, thickeners, bi.nders or fertilisers.
The compounds of the formula I are used either in an unmodified
form or preferably together with auxiliaries customarily employed in
formulation practice, and are thus processed in a known manner for example
a~
~7-
into the form of emulsion concentrates, brushable pastes, directly
sprayable or dilutable solutions, diluted emulsions, wettable powders,
soluble powders, dusts or granulates, and also encapsulations in for example
polymeric substances. The application processes, such as spraying, atom-
ising, dusting, scattering, brushing or pouring, and ]ikewise the type of
composition, are selected to suit the objectives to be achieved and the
given conditions. Favourable applied amounts are in general between 10 g
and 5 kg of active substance (AS) per hectare, preferably between 100 g and
2 kg as AS per hectare, and in particular between 200 g and 600 g of AS
L0 per hectare.
The formulations, that is to say, the compositions or preparations
containing the active substance of the formula I and optionally a solid or
liquid additive, are produced in a known manner, ~or example by the intimate
mixing and/or grinding of the active substances with extenders, such as
with solvents, solid carriers and optionally surface-active compounds
(tensides). These measures are familiar to one skilled in the art.
Suitable sol-vents are: aromatic hydrocarbons, pre~erably the
fractions C~ ~o Cl2, such as xylene mixtures or subs-tituted naphthalenes,
phthalic esters, such as dibu~yl-or dioctylphtha]ate, aliphatic hydrocarbons,
2n sucll as cyclohe~ane or paraffins, alcohols and glycols, as well as ethers and
esters thereof, such as ethanol, ethylene glycol, ethylene glycol mono-
methyl or -ethyl ether, ketones, such as cyclohexanone, strongly polar sol-
vents, such as N-methyl~2-pyrrolidone, dimethyl sulfoxide or dime~hyl
formamide, and also optionally epoxidised vegetable oils, such as epoxidised
coconut oil or soybean oil; or water.
The solid carriers used, :for example for dus~s and dispersible
--8--
powders, are as a rule natural mineral fillers, such as calcite, talcum,
kaolin, montmorillonlte or attapulgite. To improve the physical properties,
it is also possible to use highly dispersed silicic acid or highly dispersed
absorhent polymers. Suitable granulated adsorptive carriers are porous
types, for example: pumice, ground brick, sepiolite or bentonite; and suitable
nonsorbent carriers are for example calcite or sand. In addition, a great
number of pre-granulated materials of inorganic or organic nature can be
used, such as in particular dolomite or ground plant resiclues.
Suitable sllrface-active compounds are, depending on the nature
oE the active substance of the formllla I to be formulated, nonionic,
cationic and/or anionic tensides having good emulsiEying, dispersing and
wetting properties. By '~ensides' are also meant mixtures of tensides.
The tensides customarily used in formulation practice are
described, inter alia, in the Eollowing publications: "Mc Cutcheon's
Detergents and Emulsifiers Annual", MC Publishing Corp., Ringwood, New
Jersey, 1980, and Sisely a~d Wood, "Encyclopedia oE Surface Active Agents",
Chemical Publishing Co., Inc. New York, 1980.
The agrochemical preparations contain as a rule 0.1 to 99%,
particularly 0.1 to 95%, of active substance of the formula I, 99.9 to 1%,
7() especially 99.8 to 5%~ of a solid or liquid additive, and 0 to 25%~ iTI
particular 0.1 to 25%, oE a tenside. Whereas commercial products are
preferably in the form of concen~rated compositions, the compositions
employed by the end-user are as a rule diluted.
The following Examples serve to further illustra~e the invention
without limiting the scope thereof. Tempe:rature values are given in degrees
Centigrade, and percentages and 'parts' relate to weigl~k. RT = room temp-
erature and absolute = anhydrous.
_9_
Production Examples - Examples 1 ;llustrates the process steps used to
produce the compounds of the invention.
Example 1: Production of
CH2-~
Cl~ CH2 _ N ~ NaH/BrCH2C6H5 ~ ~ '
! I\~ (KI) i 2 ~N
C~ 7 n
~ C3H7-n (2)
l-(lH-1,2,4-Tri.azol-l-yl~-2-benzyloxy-2-(2,~-dichlorophenyl)-pentane
To a suspension of 2.4 g of 55% sodium hydride in 100 ml of
absolute DMF (adhering mi:neral oil is ~ashed away beforehand w.ith hexane~
is added dropwise, in a nitrogen atmosphere, a solution of 15 g of l-(lH-
1,2,4-triazol-1-yl)-2-(2,4-dichlorophenyl)-pentan-2-ol in ~10 ml of absolute
DMF and 10 ml of absolute THF. After ~he exothermic reaction has s-ubsided,
stirring is maintained for 1 hour at 50C, and 1 g of potassium iodide is
subsequently added. There are then added dropwise 9.6 g of benzyl bromide
in 10 ml of D~IF; the rea.ction mixture is stirred at RT :Eor 12 hours, and is
af~erwards poured ;nto ice-water. The cloudy emulsion is saturated with
sodium chlor;de, and repeatedly extracted with ethyl acetate. The combined
extracts are washed with semi-saturated sodium chloride solution, dried
over sodium sulfate, Eiltered~ and concentrated by evaporation. The residue
is puriied by column-chromatography (silica gel/dichloromethane). The Eirst
fraction yields 15 g of a yellowish oi]..
Analysis:
calculated: C = 61.55% ~1 = 5.45% N = 10.77% Cl = 18.17%
found : C = 61.6% ll - 5.7% N = 10.5% Cl = 18.0%.
3~
-10-
The following Table contains the aforementioned compoullds, and
also further compounds which can be similar]y produced by one of the
processes described in the foregoing.
Table 1: Compo-unds of the formula
1 3 X ~.
R ~ CH -N
.....
Compound Rl R2 ! R3 X PhysicalO
No. const. [ C]
1 C6H4C1(4) cyclohexyl CH3 N m.p.ll8-119
2 C6H3C12~2,4) C3H7~n ~CH -C6H N oil
3 C6H4C1(4) cyclohexyl CH2-C6H5 N m.p.ll6-118
4 C6H3C12(2,4) C3H7-n ;c}l3 N b p 170-175/
C6H~F(4) cyclohexyl CH3 N m.p~100-101
6 C6H4F(4) Icyclohexyl CH2-C6H5 N m.p. 74-75
7 C6H3C12~2,4) cyclohexyl C2H5 ; N
8 C6H3C12(2,4) ~C3H7-n CH2CH=CH2 N oil
9 C6H3C12(2~4) C3H7-i CH3 0 03 mbar
C6 3 2( ~ ) CH3 CH2-CH=CH2~ N m.p. 68-70
11 C6H3C12(2,4) CH~ 2 6 4 ( )
12 1c6H3cl(2)Br(4) CH3 Cl13 N oil
13 C6H~Cl(4) 3 7 CH3 N b p 245-2S0/
_.
~$~
Compound Rl R2 R X Physical
No. 3 conts.~C~
14 C6H3C12(2,4) C4Hg-n CH3 N b p 240-250/
C6H3C12(2,4) C4H9 n CH2-C6H5 N
16 C6~13C12(2'4) 4 9 CH2-C6H4Cl(4) N oil
17 C6H~C1(4) C4Hg-n C~13 N b.p.l85-195/
0.01 mbar
18 C6H4Cl(4) C4Hg-n C~12-C6H5 N oil
19 C6H3C12(2,4) CH3 CH3 N oil
C6H3C12(2,4) CH3 CH2-C6H5 N oil
21 C6H3C12(2,4) CH3 CH2-C6H4Cl(4) N oil
22 C6H3C12(2,4) CH3 C4Hg-n N oil
23 C6114Cl(4) cyclopentyl CH3 N
24 C6H3Cl2(2,4) cyclopentyl CH3 N oil
C6H3C12(2,4) cyclopentyl CH2-C6ll5 N
26 C6H3C12(2,4) cyclopentyl CH2C6H3C12(2,4) N
27 C6H3C12(2,4) cyclopent~yl C4H9-n N
28 C6H4F(4) cyclobutyl CH3 N oil
29 C6ll~Cl(4) C3H7-n CH2C6H5 N b p 170-176/
C6H3C12(2,4) cyclohe~yl CH3 0 1 mbar
31 C6H3C1(2)F(4) CH3 CH3 N oil
32 C6H3C1(2)F(~) C~13 CH2C6H~ N b.p.250/0.04
mbar
33 C6H3Cl(2)Br(4) C~13 CH2C6H5 N b.p.219/0.02
mbar
!
-12-
Com- Physical
poNuO-nd Rl R2 R3 X const.~ C]
34 C6H3Cl2~2,4) CH3 C3 7 N m.p.62-64
C H Cl (2,4) CH CH -C-CH N b.p.165-1759
6 3 2 3 C~3 0.02 mbar
36 6 3 2( ' ) CH3 2 H CHCH3 N b p 190-2009
37 C6H3C12[2,4)C3H7~n CH -C-CH2 0 02 mbar
38 C H Cl (2,4)C3H7~n Cll2CH=C1lCH3 N b.p.l80-1909
6 3 2 0.02 mbar
39 C6H3C12~2,4) 3 7 C3H7 n N oil
C6H3Cl2(2,4)C3H7~n C4H9-n N b p 189-1959
41 C6H3Cl(2)F(4) C3 7 CH2-CH=CH2 mbar
42 C6H3C1(2)F(4) C3 7 3 7 mbar
43 C6H3C1(2)F(4)C3 7 rl CH3 mbar
44 C H Cl(2)F(4) C2H5 Cil3 N b.p.l48-153/
6 3 0.02 mbar
C6l-l3C1(2)F(4)C2H5 CH2-CH=CH2 0 03 mbar
46 C6H3C12(2,4) C2H5 CH3 0 04 mbar
47 C H C12(2,4) C2H5 C3H7-ll N b~p.192-198/
6 3 0.03 mbar
48 C6H~F(4) C2H5 C4H9-n N oil
.
-l3-
CompoundRl R R X Physical
No. 2 3 const.[C]
49 C6H~F(43 C2H5 -CH2CH=CHCH3 N oil
C6H4F~4) 3 7 c3 7 N oil
51 6 ~ ( ) Cl13 Cl-l2-C6H4Cl(4) N oil
52 C6H4F(4) C2~-l5 Cl13 oil
Formulation examples for active subs~ances of the formula I
(% = per cen~ by weight) (MG = molecular weight)
Emulsion concentrates/wettable powders a) b) c)
active substance from Table 1 25% 40% 50%
calcium dodecylben~enesulfonate5% 8% 6
caster oil-polyethylene glycol 5%
ether (36 mols of ethylene oxide)
tributylphenoyl-polyethylene glycol - 12% 4%
etller (30 mols of ethylene oxide)
cyclohexanone - 15% 20%
xylene mixture 65% 25% 20%
Emulsions o any required concentration can be produced from
concentrates of this type by dilution with water. Wettable powders are
produced when xylene is replaced wi~h s;licic acid and/or kaolin.
Solutions a) b) c) d)
active substance from Table 1 80% 10% 5% 95%
ethylene glycol-monomethy] ether 20%
polyethylene glycol MG 400 - 70% _ _
N-methyl-2-pyrrolidone _ 20%
epoxidised COCOllUt oil - - 1% 5%
ligroin (boillng limits 160 - 190C) - - 9~%
The solutions are suitable for application in the form of very
small drops.
Granulates a) b~
active substance from Table 1 5% 10%
kaolin 9~%
highly dispersed silicic acid 1~ -
attapulgite - 90%
The active substance is dissolved ;n methylene chloride7 the
solution is sprayed onto the carrier, and the solvent is subsequently
evaporated off in vacuo.
Dusts a) b)
active substa.nce from Table 1 2% 5%
highly dispersed silicic acid 1% 5%
talcum 97%
kaolin - 90%
Ready-:Eor-use dusts are obtained by the intimate mixing together
:In o:E the carr;ers with the active substance.
I~iologicalExamples
Example 2.1 Action against Puccinia graminis Oll wheat
a) Residua]. protective action
Six days after being sown, wheat plants were sprayed with a spray
liquor prepared from wettable powder of the active substance (0.002% of
active substance). After 24 hours, the treated p:lants were infested with a
uredospore suspension of the fungus. After an incubation time of ~8 hours at
~ .
37
-15-
abowt 20C with 95-100% relative hum;d;.ty~ the infested plants were kept
in a greenhouse at about 22C. ~n assessment of the development of rust
pustules was made 12 days a:Eter infestation.
b) Systemic action
A spray liquor prepared from wettable powder of the active
substance (0~0006%oE active substance, relative to the volume of soil) was
poured onto the soil of wheat plants 5 days after sowing. After 48 hours,
the treated plants were infes~ed with a uredospore suspension of the fungus.
A:Eter an incubation time of ~8 hours at about 20C with 95-100% relative
:L0 humidlty, the infested plants were kept in a greenhouse at about 22C. An
assessment of the development of rust pustules was made ].2 days after
infestation.
Compounds :Erom the Table 1 exhibited against Puccinia fungi a
good action. Untreated but infested control plants displayed a level of
Pucci.nia infection Oe 100%. Puccinia infection was reduced to 0 to 5% by,
in.ter alia, the compounds Nos. 1-6, 8-14, 17, 19-22, 28~ 29, 31-43 and
50-52.
Exampl.e 2.2: Actlon against Cercospora arachidicola on groundnut plants
Residual protective actio.n
~() Groundnut plants lO-15 cm in height were sprayed with a spray
liqllor produced from wettable powder of the active substance (0.006% of
active substance); ancl 48 hours later they were infested with a conidiospore
suspension of the :Eungus. The infes~ed plants were incubated for 72 hours a~
about 2~C with high relative humidity, and were subsequently kept in a
greenhouse until the typical leaf spots had appeared. The assessment of the
fungicidal a.ction was made 12 days after l.nfestation, and was based on the
-L6-
number and size of the occurring spots.
Compared witll untreated, but infested control plants (number and
size of spots = 100%), groundnut plants wh-ich had been treated with active
substances from Table I exhibited a greatly reduced le~el of Cercospora
infection. Thus the compounds Nos. 1, 2, 3-6, 8-10, 12-1~, 17-22, 31, 33
and 3~-52 prevented the occurrence of spots in the above test vlrtually
completely (0 to 10%).
Example 2.3: Action agaillst Erysiphe graminis on barley
a) Residual protective action
Barley plants about 8 Gm in height were sprayed with a spray
liquor prepared from wettable powder of the active substance ~0.002% of
active substance). AEter 3-~ 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 extent of fungus infection was assessed
after l0 days.
b) Systemic action
A spray liquor prepared from wettable powder of the active
substance (0.0006%oE active substance, relative to the volume oE soil) was
poured OlltO the soil of barley plants about 8cm in height. Care was taken to
ens~lre that the spray liquor did not come into contact with the parts of the
plants above the soll. After ~8 hours, the treated plants were dusted with
conicliospores of the fungus. The infested barley plants were kept in a gre~n-
house at about 22C, and an assessment of the extent of ~ungus infection was
made after 10 days.
Compounds of the formula I exhibited a good action against
Erysiphe fungi. Ilntreated but infested control plants showed a level of
5~
-17-
Erysiphe infection of 100%. Among other compounds from the Table I,
compounds Nos. 1-14, 16-22, 2~, 29, 31-52 reduced Eungus infection on
barley to 0-5%. The compounds Nos. 1, 2,4-6, 8-10, 12-1~, 17, 19-21, 29,
33-43 and 50 were particularly effective (no infection).
Example 2.4: Residual protective action agalns~ ~enturia inaequalis on
applé shoots
App]e seedlings having 10-20 cm long fresh shoots were sprayed
with a spray liquor prepared from wettable powder of the active substance
(0.006% of active substance). The treated plants were sprayed after 24
1() hours with a conidiospore suspension of the fungus. The plants were then
incubated for 5 days with 90-100% relative humidity, and for a further L0
days they were kept at 20-24C in a greenhouse. The extent of scab infection
was assessed 15 days after infestation. Control plants were infected to
the extent of 100%. Compounds Nos. 1,2~4,5,12-14,17,19-21,28,29,31,
33-43 and 50 reduced infection to less than 10%. Where treatment was
carried out with the active substances ~os. 2, ~, 5, 12, 14 and 3~-43 no
infection at all occurred.
Example 2.5: Action against Botrytis on apples
Residual protective action
2() Artificially damaged apples were treated ~y applying drops of
spray liquor, prepared from wettable po~der of the active substance (0.02%
of active substance), ~o the damaged areas on the apples. The treated fruit
was then inoculated with a spore suspension of Botrytis cinerea, and
incubated for one week at about 20C with high relative humidity. The
presence and tlle size of the decayed areas on the fruit served as a basis for
assessing the extent of fungicidal activity. AEter treatment with the comp-
olmds Nos. 2~ 4, 6, 8, 10~ 12, 14, 17, 19~ 21, 28 and 31 there were no, or
virtually no, areas of decay to be observed (0-5% infection).
