Note: Descriptions are shown in the official language in which they were submitted.
596
Ihe present invention relates to trichlorovinyl ketone derivatives
of the formula
OH O Cl Cl
1 C - C = C - Cl
2 ~ ~IV)
R3
wherein
R2 and R3 are each independently hydrogen, fluorine, chlorine,
bromine, Cl-C4-alkyl, trifluoromethyl or nitro~
As alkyl are meant the groups: methyl, ethyl, propyl and butyl,
and also isomers thereof, such as iso-propyl, iso-butylJ sec-butyl and tert-
butyl.
The compounds of the formula IV are highly effective microbicides.
The compounds IV of the invention can be produced by reacting a
compound of the formula II
R2
R3 ~ oR6 ~II)
wherein R2 and R3 have the meanings defined under the formula I~, and R6 is
hydrogen or preferably methyl, with trichloroacrylic acid chloride of the
formula
Cl - C ~ C = C - Cl
" ' ' ~III)
o Cl Cl
11~6~916
in the presence of a Lewis acidO
The compounds IV of the invention are also useful as intermediates
in the production of microbicidal 2,3-dichloro-7-hydroxy-lH-inden-l-one
compounds of the formula:
OR O
R2~ Cl (I~
: R3
wherein
Rl represents hydrogen or a group of the formula -CONHR47 -COOR5,
-COSR5 or -COR4;
wherein R4 is hydrogen, Cl to C6-alkyl or C2 to C4-alkenyl, each of
which is unsubstituted or substituted by halogen or R4 is phenyl ~hich is
unsubstituted or substituted by Cl to C4-alkyl, Cl to C4-alkoxy, halogen,
trifluoromethyl, cyano or nitro, or R4 is a C3 to C6-cycloalkyl group, and
R5 represents Cl to C6-alkyl, C3 to C6-cycloalkyl or C2 to C4-
:~ alkenyl,
which are the subject of our copending application Serial NoO 339Q94, filed
November 2, 1979, of which the present application is a divisional.
The compounds I can be prepared by reacting a compound of formulaIV in the presence of a Lewis acid, to give a compound of formula V
R2~ ~ ~Cl (V)
Cl
R3
596
which corresponds to a compound of formula I wherein Rl is hydrogen; and
in order to produce compounds of formula I wherein Rl has a meaning other
than hydrogen, reacting the compound of formula V with an acid halide,
isocyanate, haloformic acid ester or halothioformic acid ester, corresponding
in each case to the meaning of Rlo
The above processes are optionally performed in the presence of
solvents inert to the reactantsO Suitable solvents for preparing the compound
of formula IV are for example: anhydrous halogenated hydrocarbons such as
chloroform, methylene chloride, carbon tetrachloride, and also carbon disulfide.
Suitable solvents for preparing the compound of formula V are for example:
nonreactive aromatic hydrocarbons, such as trichlorobenzene or nitrobenzene;
and this reaction may also be performed with the reactants forming an anhydrous
meltO Suitable solvents for introducing a group Rl are for example: (i) in
the case of acid halides and halo(thio)formic acid esters: aliphatic or
aromatic hydrocarbons such as benzene, toluene, xylenes or petroleum ether;
halogenated hydrocarbons, such as chlorobenzene, methylene chloride, ethylene
chloride or chloroform; ethers and ethereal compounds, such as dialkyl ether,
dioxane or tetrahydrofuran; nitriles such as acetonitrile; N,N-dialkylated
amides, such as dimethylformamide; dimethyl sulfoxide, ketones, such as methyl
ethyl ketone; and mixtures of solvents of this type; and acid-binding agents
may be added, for example the hydroxides, carbonates, and so forth, of alkali
metals and alkaline-earth metals, or nitrogen bases, such as pyridine and
trialkylamines; and (ii) in the case of the isocyanates: anhydrous solvents,
such as ethers, tetrahydrofuran, dioxane or dimethylformamide, and, as
catalyst, trialkylaminesO
Suitable Lewis acids are for example customary representatives such
S96
as boron trifluoride, titanium tetrachloride, tin tetrachloride, iron (III)
chloride (anhydrous) and zinc chloride~ particularly however aluminium
trichloride.
The reaction temperatures for the preparation of the compound IV are
between 20 and 120C, for the preparation of compound V between 130 and 180C,
and for the introduction of group Rl between 0 and 180C. The processes are
performed under normal pressure.
By using two equivalents of Lewis acid, relative to acid chloride
and aromatic hydrocarbons, at the commencement of the reaction, with a
temperature of 130 - 180C, it is possible to progress from compounds II and
III to compound V in a single-vessel processO In this case too the preferred
Lewis acid is AlCl30
In a modification of the process described above, it is possible in
the case of those compounds of formula I wherein R2 in the 6-position is not
hydrogen to introduce this substituent advantageously after completion of
stage b) into a compound of the formula Va
A~ Cl (Va~
by known methods of aromatic substitution. This applies for nitro and halogen.
With compounds of the formula II wherein R2 is in the meta-position,
the Friedel-Crafts reaction results in a product which is not homogeneous,
because the reaction yields, in addition to the actual compound of the formula
IV, when R3 = H, two isomeric compounds of the formulae IVa and IVb, and, when
R3 ~ H, one isomeric compound IVa
Cl Cl O OH OH
(IVa) ~ (IVb)
R3 CO - C = C - Cl
Cl Cl
which lead to undesired and/or undefined final products. Their removal from
the further course of reaction is effected for example by column chromato-
graphy.
The compounds of formula IV can be isolated at temperatures below
100C and/or with shorter reaction times (<1 hour).
Gnly with a higher temperature, longer duration and an excess of
Lewis acid (AlC13) are there formed the compounds of the formula V by inner-
lQ molecular Friedel-Crafts alkenylation in the single-vessel process already
mentionedO
The compounds of formula IV are novel and have a remarkable fungicidal
and bactericidal action. They can moreover be used for producing polymers and
copolymers and as dye-coupling components.
The said compounds IV can also be obtained by reaction of a compound
of formula VI
qH
2 ~ (Vl)
in the presence of a base, with trichloroacrylic acid chloride. There is
5~6
firstly formed the following compound
OH O-CO-C-C/
~ Cl~ & 1 base ~ ~Cl
2 ~ (VI) ~ C = C\ ) 2t~ ~VII)
R3 R3
The desired compound IV is obtained by a Fries displacement from VII, in the
presence of a Lewis acid ~preferably aluminium trichloride), in an inert
solvent.
The substituted anisoles of the formula II are commercial synthetics,
or they can be produced for example from the corresponding phenols by methyl-
ation with dimethyl sulfate, trimethyl phosphate, or the like.
The compounds of the formula IV 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 agentsJ adhesives, thickeners, binders or
fertilisers. Compositions of this type are produced, in a manner known per se,
by intimate mixing and grinding of the constituents. For application, the
compounds of formula IV can be in the following forms ~the weight-percentage
values in brackets signify advantageous amounts of active substance).
solid preparations: dusts and scattering agents ~up to 10%); granulates
[coated granules, impregnated granules and homogeneous
granules~ or pellets ~1 to 80%);
liquid preparations:
a) water-dispersible concentrates of active substance:
-6-
1~65~6
wettable powders and pastes (25 - 90% in the commercial
packing, 0.01 - 15% in ready-for-use solutions); emulsions
and solution concentrates (10 - 50%, 0.01 - 15% in ready-
for-use solutions);
b) solutions and aerosols.
The content of active substance in the above described compositions
is between Ool and 95 per cen~ by weight. Compositions of this kind are
likewise subject matter of the present invention~
In order to adapt them to prevailing circumstances and to broaden
their sphere of action, the compounds of formula IV can of course be used
together with other suitable pesticides, for example with fungicidesJ bacteri-
cides, insecticides, acaricides or herbicides, or with active substances
influencing plant growthD Such compositions too form part of the subject
matter of the present inventionO
The compounds of formula lV exhibit a very favourable microbicidal
spectrum for practical requirements for the protection of cultivated plants,
~ithout affecting the plants disadvantageously by producing undesirable
secondary effectsO Cultivated plants within the scGpe of the present invention
are for example: cereals, maize, rice, vegetablesJ sugar beet, soya bean,
groundnuts, fruit trees, ornamental plants, grape vines, hops, Cucurbitaceae
~cucumbers, pumpkins and melons), Solanaceae, such as potatoes, tobacco and
tomatoes, as well as bananas, cocoa and natural rubber 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 formulae
I and IV, and also parts of plants subsequently growing remain preserved from
5~6
such fungiO The active substances are effective against phytopathogenic
fungi belonging to the following classes: Ascomycetes ~for example Venturia,
Helminthosporium and Fusarium); Basidiomycetes, such as in particular rust
fungi (for example Puccinia and Tilletia); Fungi imperfecti (for example
Botrytis, Piricularia and Cercospora); and against Oomycetes belonging to the
Phycomycetes class, such as PlasmoparaO The active substances are also
effective against phytopathogenic bacteria, for example Pseudomonas spp. and
Xanthomonas sppO, as well as Erwinia and CorynebacteriumO Furthermore, the
compounds of the invention have in some cases a systemic action. They can
also be used as dressing agents for the treatment of seed (fruit, tubers and
grain), and of plant cuttings to protect them against infections, and also
against phytopathogenic microbes occurring in the soil. The present
invention relates therefore also to the use of compounds of formula IV for
combating microorganismsO
Preferred compounds of the invention are those in which R2 is in the
6-position and is hydrogen, nitro or halogenO
Of interest also are compounds of formula IV wherein
R2 is hydrogen or (in the 6-position) nitro, fluorine, chlorine
or bromine, or (in the 5-position) fluorine, chlorine or bromine, and
R3 is hydrogenJ fluorine, chlorine or bromine or Cl-C4-alkyl.
The Examples which follow serve to further illustrate the invention
without limiting the scope thereof. Some of the ~xamples relate to the
preparation or use of the indenones of formula I and are included for
reference purposesO The temperature values are given in degrees Centigrade,
pressure values are in millibars, and 'parts' and percentage values relate
to weight.
6596
Production Examples
Example 1 (single-vessel process)
Production of 2,3-dichloro-7-hydroxy-4-methyl-lH-inden-l-one
of the formula
OH O
~Cl
CH3
122 g of p-cresol-methyl ether and 194 g of trichloro-
acrylic acid chloride were dissolved in 500 ml of 1,2,4-
trichlorobenzene. To the stirred mixture was added 330 g
of anhydrous aluminium chloride in portions, in the course
of which the temperature rose to about 50 . The tempera-
ture was then raised to 80, with a uniform stream
of hydrogen chloride being released. The temperature was
finally raised to 120, and the mixture was stirred for a
further 4 hours. After cooling, the dark-brown reaction
mixture was introduced into ice-water, whereupon 140 g of
yellowish-brown crystals precipitated. The filtrate was
extracted with methylene chloride. On removal of the
solvent and trichlorobenzene by evaporation in vacuo, there
remained a further 60 g of crude product. The crude
substance was recrystallised from cyclohexane using actlve
charcoal. The yield was 180 g of orange-red crystals,
m.p. 178-180C.
1~4659~
- 10 -
Example 2
Production of 2,3-dichloro-4-methyl-7-methylcarbamoyloxy-
lH-inden-l-one of the formula
O -CO~HCX3
O
~Cl
Cl
CH3
229 g of 2,3-dichloro-7-hydroxy-4-methyl-lH-ind2n-l-one
was dissolved in a mixture of 1 litre of diethyl ether
and 1 litre of tetrahydrofuran, and 1 ml of triethylamine
was added. 69 g of methylisocyanate was added dropwise
to this solution at 20, the temperature rising to 28.
Crystallisation commenced after about 2 hours. After 20
hours, the crystal mass was filtered off under suction
and washed with diethyl ether. The yield was 220 g of
orange-yellow needles, m.p. 189-190 (decomposition).
Example 3
Production of 2,3-dichloro-7-hydroxy-4-methyl 6-nitro-
lH-inden-l-one of the formula
0~1 0 '
N02 ~b,C 1
I Cl
c~3
23 g of 2,3-dichloro-7-hydroxy-4-methyl-lH-inden-l-one
was suspended in 250 ml of glacial acetic acid, and this
mixture was warmed to 40 with stirring. There was then
slowly added dropwise 10.5 g of 65% nitric acid (d = 1.4),
whereupon a clear deep-~7ellcw solution was formed, an~
the reaction mixture was stirred at 40 for a further 3
S9~i
hours. After standing for 15 hours, the mixture was stirred up with 500 ml of
~ater; the yellow crystals were then filtered off with suction, and recrystal-
lised whilst still moist from alcoholO There was obtained 16 g of yellow
needles, mopD 168-170o
Example 4
a) Production of 5-bromo-2-hydroxyphenyl-trichlorovinyl ketone of the formula
OH Cl Cl
C - C = C - Cl
~0
Br
94 g of 4-bromanisole and 110 g of trichloroacrylic acid chloride
were dissolved in 800 ml of dichloromethane, and 99 g of anhydrous aluminium
chloride was added portionwise. The reaction mixture was then refluxed for
24 hours, with hydrogen chloride escapingO After cooling, there was slowly
added dropwise, with continuous stirring, 0O5 N hydrochloric acid until two
clear phases were formedO After concentration by evaporation, the dichloro-
methane phase yielded 130 g of a greenish oil, which was distilled under high
vacuum. The main fraction boiled at 102-105 and 0.02 mbarO The distillate
solidified to give 101 g of yellow crystals, m.p. 61-64 O
-.11--
S~6
The following further compounds of formula IV were produced in an
analogous manner;
OH
C - C = C - Cl . O
o Cl Cl b.p. 95-100 /0,012
mbar
~compound (i))
0~ .
C - C = C - Cl m.p, 55-58
O Cl Cl
CH3
(compound (ii))
OH
~ C - C = C - Cl
l J Cl Cl m,p. 59-62
F
(compound (iii))
OH
O Cl Cl mOp, 43-45
Cl
(compound (iv))
b) Production of 4-bromo-2,3-dichloro-7-hydroxy-lH-inden-l-one of the formula
~1~659/~
- i3 -
OH O
~¢Cl
Br
60 g of 5-bromo-2-hydroxy-phenyl-trichlorovinyl ketone
was dissolved in 150 ml of 1,2,4-trichlorobenzene, and
33 g of aluminium chloridewas added portionwise with
stirring. The reaction mixture was firstly heated to
80, and then slowly to 140; and after 4 hours, the
dark-bro~rn mass was decomposed with ice-water and 0.5 N
hydrochloric acid. After extraction with dichloro-
methane and removal of the of the solvent by distillation
in vacuo, a dark semicrystalline substance was obtained.
This was digested with 250 ml of ice-cold methanol and
filtered under suction; and the brown crys~alline product
was recrystallised from cyclohexane/toluene and active
charcoal. The yield was 20 g of light-yellow crystals,
m.p. 170-172.
Example 5
Production of 4-bromo-2,3-dichloro-7-methoxycarbonyloxy-
lH-inden-l-one of .he formula
0-COOC~3
I O
~Cl
Br
13 g of 4-bromo-2,3-dichloro-7-hydroxy-lH-inden-l-one
was dissolved in 200 ml of tetrahydrofuran; 5 g of triethyl-
amine was then added, and to the deep-red solution at 5-10
5~6
- 14 -
there was added dropwise 4.5 g of chloroformic acid methyl
ester. The reaction mixture was stirred at room tem-
perature for a further 3 hours; the triethylammonium
chloride was subsequently filtered off with suction
and the filtrate was evaporated off in vacuo. The
crystalline product was recrystallised from ethanol to
yield 12 g of yellow crystals, m.p. 135-137.
The following compounds of the formula I can be
produced in an analogous manner or by one of the methods
described herein:
Table I (Rl - H)
Comp. No. R2 R3 Physical
constants
1.1 H H m.p. l47-148
1.2 H CE3 m.p. 178-180
1.3 ~ F m.p. 171-173
1.4 H Cl m.p. 170-171
1.5 H Br m.p. 172-173
1.6 6-~02 CH3m.p. 1$8-170o
1. 7 6-Br c~3 m.p. 133-135
1.8 6-~2 Cl m.p. 147-149
1 . ~ 6-Cl Cl
1.10 5-F H
l. ll 5^Cl H
~6596
- 15 --
Table II
Comp R2 R3 R1 Phys ical
No. constants
2.1 H CH3 -CO~'HCH3 m.p. 190 (decomp.)
2.2 H CH3 -CO~-~C1 m.p. 152-1;4
2.3 H CH3 -COI~HC4H9(n) m.p. 141-143
2.4 H CH3 -COOCH3 m.p. 136-138
2 . 5 H C1 -C:ONHCH3 m . p . 180 -182
2.6 H C1 -COSC2X5 m-p- 85-88
2 . 7 H C1 -CO -C~I=CX2 m . p . 153 -155
2 . 8 H CH3 -CO-CCl=CC12 m .~p . 116 -118
2 . 9 H F -CO~ICH3 m . p . 216 -218
2 . 10 H Br -COOCH3 m . p . 135 -137 "
2.11 H C1 -COCH3 m.p. 115-117
2.12 H F -COCE12C1 m.p . ~ 43-1aS
2 . 13 6 N2 H3 -CONH-CH3 m . p . L5 9 -161
2.14 H CH3 -CONH-C H m.p. 186-188~
5~6
- 16 -
Formulation E~amples
Dust: The following substances are used to produce a) a
5% dust and b) a 2% dust:
a) 5 parts of active substance,
parts of talcum;
b) 2 parts of active substance,
1 part of highly dispersed silicic acid, and
97 parts of talcum.
The active substances are mixed and ground with the
carriers, and in this form they can be applied by dusting.
Granulate: The following substances are used to produce a
5% granulate:
parts of active substance,
0.25 part of epichlorohydrin,
0.25 part of cetyl polyglycol ether,
3.50 parts of polyethylene glycol, and
91 parts of kaolin (particle si~e 0.3 ~ 0.8 mm~.
The active substance is mixed with epichlorohydrin
and dissolved in 6 parts of acetone, and the polyethylene
g~ycol and cetyl polyglcol ether are then added. The
solution obtained is sprayed onto kaolin, and tne acetone
is evaporated off in vacuo. A microgranulate of this
type is advantageously used for combating soil fungi.
Wettable powder: The following constituents are used to
produce a) a 70% wettable powder, b) a 40% wettable powder,
c) and d) a 25% wettable po~der, and e) a 10% wettabl2
powder:
a) 70 parts of active substance,
parts of sodium dibutylnaphthylsulfonate,
3 parts of naphthalenesulfonic acid/phenolsulfonic
acid/formadehyde condensate (3:2:1),
fi596
- 17 -
parts of kaolin, and
12 parts of Champagne chalk,
b) 40 parts of active substance,
parts of sodium lignin sulfonate,
1 part of sodium dibutylnaphthylsulfonate, and
54 parts of silicic acid;
c) 25 parts of active substance,
4.5 parts of calcium lignin sulfonate,
1.9 parts of Champagne chalk/hydroxye~hyl 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;
d) 25 parts of active substance,
2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol,
1.7 parts o~ Champagne chalk/hydroxyethylcellulose
mixture (1:1),
8.3 parts of sodium aluminium silicate,
16.5 parts of kieselgur, and
46 parts of kaolin; and
e) 10 parts of active substance,
3 parts of a mixture of the sodium salts of
saturated fatty alcohol sulfates,
parts of naphthalenesulfonic acid/formaldehyde
condensate, and
82 parts of kaolin.
The active substances are intimately mixed in suitable
mixers with the additives, and the mixture is then ground
in applicable mills and rollers. There are obtained
wettable powders which have excellent wetting and suspen-
sion properties, which can be diluted with water to ~ive
suspensions of the deslred concentration, and which in this
form are particularly suitable for leaf application.
~14f~596
- 18
Emulsion concentrate: The following substances are used
to produce a 25% emulsifiable concentrate:
parts of active substance,
2.5 parts of epo~idised vegetable oil,
parts of an alkylarylsulfonate/fatty alcohol
polyglycol ether mixture,
parts of dimethylformamide, and
57.5 parts of xylene.
Emulsions of the concentration desired can be prepared
from these concentrates by dilution with water, and they are
particularly sultable for leaf application.
Biolo~ical Examples
Example 6
Act-on 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 (0.068/c 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) S~stemic 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
S days after sowing. After 48 hours, the treated plants
were infested with a uredospcre suspension of the fungus.
~ ~6596
- 19 -
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.
Example 7
Action a~ainst 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 7Z hours
at about 21C with high relative humidity, and were
subsequently kept in a greenhouse until the typical leaf
spots has 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 a~ainst Botrvtis cinerea on broad beans
Broad bean plants about 10 cm in height were sprayed
with a spray liquor produced from wettable powder of the
active substance (0.02% of active substance); and after
2~ hours, the treated plants were infested with a conidio-
spore suspension of the fungus. After incubation of the
infested plants for 2-3 days with 95-100% relative humidity
at 21C, an assessment of the extent of fungus infection
was made.
.,,
6596
- 20 -
Example 9
Action a~ainst Piricularia oryzae on rice plants
a) Residual protective action
After two-weeks' cultivation, rice plants were sprayed
with a spray liquor produced from wettable powder of the
active substance (0.02% of active substance). After 48
hours, the treated plants were infested with a conidiospore
suspension of the fungus. The extent of fungus infection
present was assessed after 5 days' incubation at 24~C
with 95-100% relative humidity.
b) Systemic action
A spray liquor produced from wettable powder of the
active substance (0.005% of active substance, relative to
the volume of soil ) was applied to the surface of the
soil of two-week-old rice plants. The pots were then
~illed with water to the extent that the lowest parts of
the stalks of the rice plants were in water. After 48
hours, the treated plants were infested with a conidiospore
suspension of the fungus. After incubation of the plants
during 5 days at about 24C with 95-100% humidity, the
degree of fungus infection was assessed.
Examele 10
Action a~ainst Tilletia caries
.~
Tilletia spores were suspended in a spray liquor
containing 600 ppm of active substance for 15 minutes.
The spore/active substance mixture was applied dropwise
by pipette to the surface of finely sieved moist soil in
Petri dishes. The soil dishes prepared in this way were
kept at a temperature of 20~C with high relative humidity.
After abcut 10 days, spore germinatlon was assessed under
a microscope. The action of the test substances was
5~6
assessed on the basis of the number and length of the germ tubesD
Example 11
Action against Plasmopara viticola on grape vines
Residual protective action
Young grape-vine seedlings in the 4-5-leaf stage 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
sporangia suspension of the fungusO After an incubation time of 6 days at
20C with 95-100% relative humidity, an assessment of fungus infection was
made.
Example 12
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)O 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.
The compounds IV according to the invention and the compounds of
formula I exhibited in general a good fungicidal action in the preceding tests.
Compared with the infection present on untreated but infested control plants,
the level of infection on the treated plants had been reduced to less than 20%
by, among other compounds of formulae I and IV, those compounds of formula I
and of the
-21-
1~465~;
22
inventiGn which are listed below:
against Puccinia graminis: Compounds Nos. 1.2, 1.3, 1.4,
1.5, 2.2, 2.5, 2.9, 2.10, 2.11, 2.12, (i),
(iii) and (iv);
against Cercospora arachidicola: Compounds Nos. 2.3, 2.5,
2.6, 2.7, 2.9, 2.10, (i) and (iv);
against ~otrytis cinerea: Compounds Nos. 1.3, 1.4, 1.5
and 2.5;
against Piricularia oryzae: Compounds Nos. 1.3, 1.4, 2.1,
2.11, 2.14, 2.9 and (iv);
against Tilletia caries: Compound No. 2.5;
against Plasmopara viticola: Compounds Nos. 1.4 and 2.1; and
against ~'enturia inaequalis: Compounds Nos. 1.4 and 2.1.
Example 13
Action a~ainst Xanthomonas oryzae on rice plants
a) Residual protective action
Rice plants of the "Caloro" or "S6" variety were sprayed
after 3 weeks' cultivation in a greenhouse with the test
substance in the form of a spray liquor (0.06% of active
substance). The sprayed-on coating was allowed to dry
for one day, and the plants were then transferred to a
climatic chamber at 24C with 75-85% relative humidity
and infected. The infection was introduced by cutting off
the leaf-tips with scissors which had previously been
immersed in a suspension of Xanthomonas oryzae. After an
incubation period of 10 days in the same chamber, the
leaves which had been cut became withered, rolled up and
became necrotic. The extent of these disease sy~ptoms
se.ved as a basis for the assessment of the residual
effectiveness of the test substance.
11~tj596
- 23 -
b) Systemic action
A suspension of the test substance (0.006% of active
substance, relative to the volume of soil) was applied,
after a cultivation time of 3 weeks, to the soil of rice
plants of the "Caloro" or "S6" variety grown in flower
pots. Three days ~fter this treatment, the plants were
transferred to a climatic chamber at 24C with 75-~5%
relative humidity and infected. The infection was imparted
by the tips of the leaves being cut off with scissors
which had previously been immersed in a suspension of
Xanthomonas oryzae. After lO days' incubation in the same
chamber, the leaves which had been cut became withered,
rolled up and became necrotic. The extent of these
disease symptoms on the test plants served as a basis
for the assessment of the systemic effectiveness of the
test substance.
In the above tests 13 a and b, the compounds of the
formulae I and IV exhibited a good action. The treated
plants displayed no symptoms of wilt or of necrosis.
Example 14
Action against Xanthomonas vesicatoria on paprika plants
a) Residual protective action
After 3-weeks' cultivation in a greenhouse, paprika
plants of the "California Wonder" variety were sprayed
with the test substance in the form of a spray liquor
(0.06% of active substance). This sprayed-on coating was
allowed to dry for one day; the plants were subsequently
transferred to a climatic chamber at 26C with 95 - 100%
relative humidity, and were infested by spraying of the
underside of the leaves ~ith a standardised suspension of
Xanthomonas vesicatoria. After an incubation time of six
114~;~96
- 24
days in the same chamber, there were formed on the
leaves of the control plants round, lighter-coloured
spots, which were initially watery and later necrotic.
The extent of these spots on the test plants served as a
basis for evaluating the residual action of the test
substance.
b) Systemic action
A suspension of the test substance (0~0~6~/o of active
substance, relative to the volume of soil) was applied,
after 3-weeks' cultivation, to the soil of paprika
plants of the "California Wonder" growing in flower pots.
Three days after this treatment, the plants were placed
into a climatic chamber at 26C with 95 - 100% relative
humidity; the plants were then infested, by spraying of
the underside of the leaves, with a standardised suspension
of Xanthomonas vesicatoria. After an incubation time of
six days in the same chamber, there were formed on the
leaves of the control plants round, lighter-coloured spots,
which were initially watery and later necrotic. The
extent of these spots serves as a basis in assessing the
systemic actlon of the test substance.
In the above tests 14 a and b, there was exhibited a
good action by, inter alia, the compounds Nos. 1.2, 1.3,
(iii) and (iv).
