Fungicidal 4-monohaloacetoacetoacetanilides

The invention concerns certain 4-monohalo-2,2-dimethyl-3-oxobutyric acid anilides substituted on the phenyl radical and the use of these compounds as fungicidal-active materials.
The use of 4-chloro-3-oxobutyric acid anilide in seed material disinfection is described by C. H. Arndt (Plant Diseases Reporter 34, p. 334 (1950), correspondingly in Chemical Abstracts, 45, 2129 (1951)). From EP-PS 7 089 (published on the 16th September 1981, N. Haberle et al., Consortium fur Elekrochemische Industrie GmbH) is known the use of 2-methylpent-4-enoic acid 3',4'-dichloroanilide and 2-methylbut-3-enoic acid 3',5'-dichloroanilide against spores of Fusarium nivale and Tilletia tritici.
It was the task of the invention to make available fungicides with broader activity spectrum. Furthermore, it was the task of the present invention to make available fungicides which manifest satisfactory action even in the case of small applied amounts. Furthermore, it was the task of the invention to prepare fungicidal-active materials with high compatibility for cultivated plants.
In the scope of the present invention, these tasks are solved by compounds of the formula ##STR2## wherein X is a halogen atom, R the same or different substituents in any desired position of the benzene ring, namely, halogen atoms, C.sub.1 -C.sub.3 -alkyl groups, trifluoromethyl groups or cyano groups and n a whole number with a value of 1, 2 or 3.
As residues X, Cl, Br, I, especially Br, are preferred.
As residues R are preferred F, Cl, Br, I, methyl groups, trifluoromethyl groups and cyano groups.
Increasedly effective as fungicides are compounds of the formula (I) in which X stands for a chlorine, bromine or iodine atom and R.sub.n signifies a trifluoromethyl radical in 3-position or, in all, 3 methyl radicals each in the 2, 4 and 6 position.

The compounds of formula (I) according to the invention can be prepared, for example, in that one reacts compounds of the formula ##STR3## wherein Y signifies a chlorine or bromine atom, with compounds of the formula ##STR4## In the formulae (II) and (III), X, R and n can, in each case, have the same meanings as in formula (I).
The reaction is preferably carried out in the presence of substances binding hydrogen halides, especially in the presence of tertiary amines. Examples of such tertiary amines are tributylamine, N,N-dimethylaniline, pyridine and the like.
The reaction is preferably carried out in a solvent. Examples of suitable solvents are acetic acid ethyl ester, acetone, diethyl ether, dioxan and the like.
In order to suppress side reactions, such as the formation of the corresponding 3,3-dimethylpyrrolidine-2,4-diones, it is recommended to carry out the reaction at relatively low temperature and in the presence of a solvent.
Temperatures of 5.degree. C. to 35.degree. C., especially of 10.degree. C. to 25.degree. C., are preferred. The solvents are preferably used substantially free of water.
Those compounds of the formula (I), in which X signifies an iodine atom, are expediently prepared by Finkelstein reaction from the corresponding compounds of the formula (I), in which X signifies a chlorine or bromine atom, i.e. by reaction with alkali metal iodide in acetone or a solvent of similar properties.
The compounds of formula (II) used as starting materials are obtainable, for example, by the reaction of dimethylketene with alpha-haloacetic acid halides according to DE-OS 33 08 175.
The starting materials of formula (III) are commercially available or can be prepared according to known processes.
In the following Tab. 1 are set out examples of the compounds of formula (I) according to the invention.
TAB. NO. 1__________________________________________________________________________active meltingmaterial sum point inNo. chemical designation formula .degree.C.__________________________________________________________________________1 4-chloro-2,2-dimethyl-3-oxo- C.sub.12 H.sub.13 ClFNO.sub.2 111 butyric acid 2'-fluoroanilide2 4-chloro-2,2-dimethyl-3-oxo- C.sub.12 H.sub.13 ClFNO.sub.2 155 butyric acid 4'-fluoroanilide3 4-chloro-2,2-dimethyl-3-oxo- C.sub.13 H.sub.13 ClF.sub.3 NO.sub.2 69 butyric acid 2'-(trifluoro- methyl)-anilide4 4-chloro-2,2-dimethyl-3-oxo- C.sub.13 H.sub.13 ClF.sub.3 NO.sub.2 90 butyric acid 3'-(trifluoro- methyl)-anilide5 4-chloro-2,2-dimethyl-3-oxo- C.sub.13 H.sub.13 ClF.sub.3 NO.sub.2 123 butyric acid 4'-(trifluoro- methyl)-anilide6 4-chloro-2,2-dimethyl-3-oxo- C.sub.13 H.sub.13 ClN.sub.2 O.sub.2 150 butyric acid 4'-cyanoanilide7 4-chloro-2,2-dimethyl-3-oxo- C.sub.12 H.sub.13 ClJNO.sub.2 62 butyric acid 2'-iodoanilide8 4-chloro-2,2-dimethyl-3-oxo- C.sub.13 H.sub.15 ClFNO.sub.2 80 butyric acid 5'-fluoro-2'- methylanilide9 4-chloro-2,2-dimethyl-3-oxo- C.sub.14 H.sub.12 ClF.sub.6 NO.sub.2 107 butyric acid 3',5'-bis-(tri- fluoromethyl)-anilide10 4-chloro-2,2-dimethyl-3-oxo- C.sub.13 H.sub.12 Cl.sub.2 F.sub.3 NO.sub.2 78 butyric acid 2'-chloro-5'- (trifluoromethyl)-anilide11 4-chloro-2,2-dimethyl-3-oxo- C.sub.15 H.sub.20 ClNO.sub.2 134 butyric acid 2',3',4'- trimethylanilide12 4-chloro-2,2-dimethyl-3-oxo- C.sub.15 H.sub.20 ClNO.sub.2 110 butyric acid 2',4',6'- trimethylanilide13 4-chloro-2,2-dimethyl-3-oxo- C.sub.12 H.sub.11 Cl.sub.4 NO.sub.2 96 butyric acid 2',3',4'- trichloroanilide14 4-chloro-2,2-dimethyl-3-oxo- C.sub.12 H.sub.11 Cl.sub.4 NO.sub.2 104 butyric acid 2',4',5'- trichloroanilide15 4-bromo-2,2-dimethyl-3-oxo- C.sub.12 H.sub.13 BrFNO.sub.2 156 butyric acid 4'-fluoro- anilide16 4-bromo-2,2-dimethyl-3-oxo- C.sub.13 H.sub.16 BrNO.sub.2 130 butyric acid 4'-methyl- anilide17 4-bromo-2,2-dimethyl-3-oxo- C.sub.13 H.sub.13 BrF.sub.3 NO.sub.2 101 butyric acid 3'-(trifluoro- methyl)-anilide18 4-bromo-2,2-dimethyl-3-oxo- C.sub.13 H.sub.12 BrClF.sub.3 NO.sub.2 78 butyric acid 2'-chloro-5'- (trifluoromethyl)-anilide19 4-bromo-2,2-dimethyl-3-oxo- C.sub.15 H.sub.20 BrNO.sub.2 123 butyric acid 2',4',6'- trimethylanilide20 4-iodo-2,2-dimethyl-3-oxo- C.sub.12 H.sub.13 FINO.sub.2 133 butyric acid 4'-fluoro- anilide21 4-iodo-2,2-dimethyl-3-oxo- C.sub.13 H.sub.13 F.sub.3 INO.sub.2 95 butyric acid 3'-(trifluoro- methyl)-anilide22 4-iodo-2,2-dimethyl-3-oxo- C.sub.15 H.sub.20 INO.sub.2 128* butyric acid 2',4',6'- trimethylanilide__________________________________________________________________________ *with decomposition.
The compounds according to the invention display fungitoxic properties. They are used against fungal attacks on plants or on plant products.
Depending upon the phenyl substitution, there are thereby achieved actions against Botrytis cinerea, against fungal spores in general, against rust fungi (e.g. bean rust=Uromyces phaseoli), against oomycetes, such as e.g. Phytophthora infestans, Plasmopara viticola, or Pythium ultimum or against Ascomycetes, such as e.g. Venturia inaequalis (=apple scab). Piricularia oryzae (leaf spot disease in rice) is also combatable with a part of the compounds according to the invention.
The active materials according to the invention are suitable, without their field of use thereby being restricted thereto, e.g. for use in viticulture, in horticulture and vegetable cultivation (especially salad cultivation and strawberry cultivation), in cereal production, in rape production, in hop production, and in stoned fruit production. On the other hand, the compounds according to the invention are not suitable for the combating of types of mildew, such as e.g. Erysiphe cichoracearum (mildew in gherkins) or cereal mildew (Erysiphe graminis).
The application of the active materials takes place in per se known manner to the living area of the fungi, for example by pouring, splashing, spraying, dusting, coating. There can be achieved not only a prophylactic but also a curative action.
The active materials according to the invention can be applied alone or in admixture with other pesticides, especially fungicidal agents. In general, they are used as mixtures with solid or liquid dilution agents or as solutions in solid or liquid solvents with active material contents of 0.005 to 95 wt.%.
In general, the mixtures or solutions are prepared as emulsion concentrates, pastes, spray powders, granulates or microcapsules.
In general, emulsion concentrates and pastes contain 10 to 90 wt.%, preferably 15 to 50 wt.% of active material, 2 to 25 wt.% of dispersion adjuvants and organic solvents and/or water.
Spray powders mostly contain 10 to 80 wt.%, preferably 15 to 70 wt.% of active material, 1 to 30 wt.% of dispersion adjuvants and 10 to 89 wt.% of inert components.
Besides inert components and/or coating materials, granulates and microcapsules contain 1 to 10 wt.%, preferably 5 to 10 wt.% of active material.
According to the invention, there are used: as dispersion adjuvants, e.g. alkyl and aryl sulphonates, methyl cellulose, polymeric sulphonic acids and their salts, polyalcohols, fatty acid esters, fatty alcohol ethers, fatty amines;
as organic solvents, e.g. alcohols, such as ethanol, butanols, dimethylformamide, dimethyl sulphoxide, N-methylpyrrolidione, aromatics, such as toluene and xylenes;
as inert components, e.g. kaolin, China clay, talc, calcium carbonate, highly dispersed silicic acid, silica gels, kieselguhr, diatomaceous earth, pumice, brick dust, coarse-ground maize, thickening agents, such as starch and carboxymethylcellulose, cyclodextrins;
as binding agents, e.g. magnesium sulphate, gypsum, gum arabic, polyvinyl alcohol.
For example, for use as fungicides, the active materials according to the invention are formulated as follows:
______________________________________Spray powder20 wt. % active material44 wt. % China clay16 wt. % highly dispersed silicic acid15 wt. % lignin sulphonate (cell pitch) 5 wt. % sodium alkylnaphthalenesulphonate- formaldehyde condensate (Atlox 4862, Registered Trade Mark, manufacturer: Atlas-Chemie, D-4300 Essen)______________________________________Emulsion concentrate20 wt. % active material30 wt. % cyclohexanone30 wt. % xylene20 wt. % Tween Twenty (Registered Trade Mark, manufacturer Atlas-Chemie, D-4300 Essen).______________________________________
The following Examples serve for the explanation of the invention. The products according to the invention were, in each case, identified by .sup.1 H-NMR spectroscopy (inner standard: tetramethylsilane).
EXAMPLE 1, PREPARATION EXAMPLE 4-Chloro-2,2-dimethyl-3-oxobutyric acid 3'-(trifluoromethyl)-anilide, active material 4
18.3 g. (0.1 mole) 4-chloro-2,2-dimethyl-3-oxobutyric acid chloride were dissolved in 150 ml. acetic acid ethyl ester and a mixture of 16.1 g. (0.1 mole) 3-trifluoromethylaniline, 10.1 g. (0.1 mole) triethylamine and 50 ml. acetic acid ethyl ester added dropwise thereto, with stirring, at 20.degree. C. within 90 min. Subsequently, for the completion of the reaction, it was further stirred for 60 min. at 35.degree. C., then the solvent distilled off, 100 ml. cyclohexane added thereto and the still warm mixture filtered. From this filtrate, the desired product crystallised out.
Yield: 27.8 g. (90.4% of theory); melting point: 69.degree. C. .sup.1 H-NMR (CDCl.sub.3): 1.6 ppm (s, 6H, 2 CH.sub.3 groups in 2-position of the acyl radical), 4.4 ppm (s, 2H, CH.sub.2 group of the acyl radical), 7.2-7.85 ppm (m, 4H, 4 arom. protons), 8.0 ppm (s, 1H, broad, NH).
EXAMPLE 2, PREPARATION EXAMPLE 4-Iodo-2,2-dimethyl-3-oxobutyric acid 3'-(trifluoro- methyl)-anilide, active material 21
22 g. (0.07 mole) of the 4-chloro derivative prepared according to Example 1 were dissolved in 15 ml. dry acetone and a solution of 10.5 g. (0.07 mole) sodium iodide in acetone added thereto. The mixture was heated to reflux for 7 hrs., then cooled and the sodium chloride formed filtered off. The filtrate was evaporated and the residue crystallised. By recrystallisation from methanol/water (4:1), the desired substance was obtained in 74.9% yield. The melting point of the compound lay at 95.degree. C.
.sup.1 H-NMR (CDCl.sub.3) 1.6 ppm (s, 6H, 2 CH.sub.3 groups in 2-position of the acyl radical), 4.1 ppm (3, 2H, CH.sub.2 group of the acyl radical), 7.15-7.9 ppm (m, 4H, 4 arom. protons), 8.1 ppm (s, 1H broad, NH).
For the following working examples, some of the known acylanilides were used as comparative agents:
1. 4-chloro-3-oxobutyric acid anilide, e.g. known from C. H. Arndt, Plant Diseases Reptr. 34, 334-347 (1950) C.A. 45, 2129t, 1951), in the following referred to as"comparison A",
2. 3-oxobutyric acid 3',4'-dichloroanilide, known as herbicide from CH 542,575, in the following referred to as "comparison B",
3. 2-methylpent-4-enoic acid 3'-chloro-4'-methyl-anilide, known from EP 7.089, in the following referred to as "comparison C",
4. 2,2-dimethylpent-4-enoic acid 3',4'-dichloroanilide, also known from EP 7.089, in the following referred to as "comparison D".
EXAMPLE 3, WORKING EXAMPLE
Spore germ test
50 .mu.l. of a solution or suspension of an active material with a content of 250 ppm of active substance were, together with 50 .mu.l. of a spore suspension, produced by slurrying of spores from an agar culture with a nutrient solution which, per litre, contained 10 g. sugar, 1 g. glycol, 1 g. KH.sub.2 PO.sub.4 and 0.5 g. MgSO.sub.4, introduced into the hollow cut-out of a hollow cut-out object slide. The object slide was stored at 20.degree. C. for 48 hours in a Petri dish, the bottom of which was covered with moistened filter paper.
Thereafter, the ratio of the germinated and of the non-germinated spores was compared against an untreated control sample. The degree of action is given in % according to the following formula: ##EQU1##
The results are summarised in the following Tab. 2.
TAB. NO. 2__________________________________________________________________________Fungitoxicity of active materials according to the invention and ofcomparativeagents at 250 ppm active material concentration in %Active Alternaria Botrytis Fusarium Fusarium Colletotrichum Verticillium Penicilliummaterial No. solani cinerea colmorum nivale coffeanum dahliae glaucum__________________________________________________________________________1 20 80 20 80 80 10 03 95 90 70 100 100 100 604 60 80 80 100 100 80 706 80 100 80 80 100 80 807 20 80 80 80 100 100 808 100 100 100 100 100 100 10010 60 90 100 100 100 100 10011 30 100 20 100 100 100 10013 100 100 90 100 100 100 10014 100 100 100 100 100 100 10015 10 100 100 100 100 100 3016 95 100 100 100 100 100 10017 100 100 100 100 100 100 10018 80 100 80 100 100 100 1019 60 100 70 100 100 100 1021 100 100 100 100 100 100 10022 30 80 30 100 100 100 10comparsion A 0 0 20 100 n.d* 0 n.d.*comparison B 0 0 10 80 n.d.* 10 n.d.*comparison C 0 10 0 100 0 0 0comparison D 0 10 0 10 10 20 0__________________________________________________________________________ *n.d. = not determined
EXAMPLE 4, WORKING EXAMPLE
Grape juice test
20 ml. of a nutrient solution of grape juice and distilled water in the ratio of 1:1 were filled into Petri dishes and mixed with the active materials given in the following Table. The active material concentration amounted to 31 ppm. Subsequently, the experimental batches were, in each case, inoculated with 50 .mu.l. of a Botrytis spore suspension, produced by slurrying of the Botyrtis spores from an agar culture with distilled water.
After a culturing period of 10 or 20 days at 20.degree. C., the extent of the fungus development on the nutrient solution surface was assessed.
The degree of action was calculated in % according to the following formula: ##EQU2##
TAB. NO. 3______________________________________ Effectiveness of compounds according tothe invention and of comparative agentsin % degrees at 31 ppm active materialconcentration after 10 or 20 days periodof actionActive material % EffectivenessNo. after 10 days after 20 days______________________________________ 8 100 10010 100 10011 100 10012 100 8013 100 10014 100 10015 100 10016 100 10017 100 10018 100 10019 100 10020 100 10021 100 10022 90 70comparison A 0 0comparison C 0 0comparison D 0 0______________________________________
Especially active compounds according to the invention, such as e.g. 13, 14, 15, 16, 18 and 20, still showed 100% effectiveness even at 8 ppm active material concentration.
EXAMPLE 5, WORKING EXAMPLE
Effectiveness against Pythium ultimum in the case of soil application.
The active material was uniformly mixed in a concentration of 500 ppm with soil which has been artificially infected with Pythium ultimum. The so treated soil was filled into plastic pots (in each case 4 repetitions per test substance) and each seeded with 10 pea seeds. These pots were kept for 10 days at 24 to 26.degree. C. and at an atmospheric humidity of 75 to 90%. Thereafter, the number of healthy, germinated plants was determined. The degree of action was calculated by comparison with infected but untreated soil samples. The results are summarised in the following Table.
TAB. NO. 4______________________________________ Effectiveness of active materials accordingto the invention and of comparative agentsin % degrees at 500 ppm active materialconcentration against Pythium ultimum.Active material No. % effectiveness______________________________________1 802 803 1004 1005 1008 8011 8019 80comparison A 20comparison B 0comparison C 25comparison D 20______________________________________
EXAMPLE 6, WORKING EXAMPLE
Effectiveness against Uromyces phaseoli (bean rust)
Young bean plants which had formed the first three-leaf sprouting (14-18 days after sowing) were sprayed dripping wet with a formulation of the active material to be tested (active material concentration 500 ppm). About 20 hours after the spraying, when the spray coating is completely dried, the plants were artificially uniformly infected with a spore suspension of Uromyces phaseoli which had been obtained from infected bean plants.
After remaining for 20-24 hours in a dark humid chamber (18.degree.--22.degree. C.; 90-100% atmospheric humidity), the test plants were kept in a greenhouse at 18.degree.-22.degree. C. and 60-80% atmospheric humidity for two weeks. Subsequently, when untreated control plants showed strong attack, the degree of attack of the test plants was ascertained.
TAB. NO. 5______________________________________ Effectiveness of active materials accordingto the invention and of comparative agentsagainst Uromyces phaseoli (bean rust) at125 ppm active material concentration.Active material No. % effectiveness______________________________________1 1002 553 904 959 8510 8011 8012 8019 90comparison A 50comparison B 0comparison C 10comparison D 15______________________________________

Number	Date	Country
0007089	Jan 1980	EPX
0088259	Sep 1983	EPX

Fungicidal 4-monohaloacetoacetoacetanilides

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