CA1146596A - Microbicidal trichlorovinyl ketone derivatives - Google Patents

Abstract

A B S T R A C T
Novel trichlorovlnyl ketones are disclosed of the formula:

Description

Ihe present invention relates to trichlorovinyl ketone derivatives of the formula OH O Cl Cl 1 C - C = C - Cl

2 ~ ~IV) 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

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 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 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) 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:

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.

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 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~

Example 2 Production of 2,3-dichloro-4-methyl-7-methylcarbamoyloxy-lH-inden-l-one of the formula O -CO~HCX3 O
~Cl Cl 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 (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 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 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 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 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 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 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.

.,, 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 1~465~;

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 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 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).

Claims (16)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A trichlorovinyl ketone derivative of the formula:

(IV) (IV) wherein R2 and R3 each independently represent hydrogen, fluorine, chlorine, bromine, C1-C4-alkyl, trifluoromethyl or nitro.

2. A compound according to Claim 1 wherein R2 is hydrogen, or is in the 6-position and is nitro, fluorine, chlorine or bromine, or is in the 5-position and is fluorine, chlorine or bromine; and R3 is hydrogen, fluorine, chlorine, bromine or C1-C4-alkyl.

3. A compound according to Claim 2, wherein R2 is hydrogen, or is in the 6-position and is nitro or halogen.

4. 5-Bromo-2-hydroxyphenyl-trichlorovinyl ketone.

5. 2-Hydroxyphenyl-trichlorovinyl ketone.

6. 5-Methyl-2-hydroxyphenyl-trichlorovinyl ketone.

7. 5-Fluoro-2-hydroxyphenyl-trichlorovinyl ketone.

8. 5-Chloro-2-hydroxyphenyl-trichlorovinyl ketone.

9. A process for combating microorganisms, which process comprises treating the microorganisms to be combated, or the habitat thereof, with a compound according to Claim 1.

10. Process according to Claim 9, wherein the microorganisms to be combated are phytopathogenic fungi.

11. Process according to Claim 9, wherein the microorganisms to be combated are phytopathogenic bacteria.

12, A process for combating microorganisms, which process comprises treating the microorganisms to be combated, or the habitat thereof, with a compound according to Claim 2, 3 or 4.

13. A process for combating microorganisms, which process comprises treating the microorganisms to be combated, or the habitat thereof, with a compound according to Claim 5, 6 or 7.

14. A process for combating microorganisms, which process comprises treating the microorganisms to be combated, or the habitat thereof, with a compound according to Claim 8.

15. A process for producing a compound according to Claim 1, which process comprises reacting a compound of formula II

(II) wherein R2 and R3 have the meanings given under the formula I, and R6 is hydrogen or methyl, with trichloroacrylic acid chloride of formula (III) (III) in the presence of a Lewis acid.

16. A process according to Claim 15, wherein R6 in formula II is methyl.